Surface treating material and surface treating process
The present invention is an object to provide a surface treating material and a surface treating process using the surface treating material capable of giving simply and effectively desired surface property on a surface of an image recording layer of an image recording material after image recording, and the surface treating material comprising at least a fusible particle and a hardly fusible particle which are used for changing a surface property on a surface of an image recording layer of an image recording material after image recording, the fusible particle is melted to form a continuous film by the surface treatment, and a flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment, and the hardly fusible particle is not melted with maintaining particle shape by the surface treatment, and a volume average particle diameter of the hardly fusible particle is 1 μm to 30 μm.
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1. Field of the Invention
The present invention relates to a surface treating material and a surface treating process using the surface treating material capable of giving simply and effectively desired surface property on a surface of an image recording layer of an image recording material after image recording.
2. Description of the Related Art
As a gloss treatment or semigloss treatment of a surface of an image recording layer of an image recording material after image recording, there is a conventional process forming a transparent overcoat layer by adhering and melting transparent particle on the surface of the image recording layer.
According to this process, gloss increases, but there are problems such as in sheet accumulation after treatment, accumulation shift occurs easily, glaringness occurs on the surface of the image recording layer, and during repeated storing, in high humidity storing, adhesion between sheets occurs, and fingerprint adhesion trace is easily noticeable.
For the semi-gloss treatment, for example, forming of non-continuous (sea-island) structure by transparent toner (Japanese Patent Application Laid-Open (JP-A) No.05-232840), a process blending particle on binding a resin of transparent toner japanese Patent Application Laid-Open (JP-A) No.10-123863), and the forming process of the uneven surface by controlling the transparent toner fixing condition (Japanese Patent Application Laid-Open (JP-A) No.2001-305816), are proposed.
In the proposal of the JP-A No.05-232840, the toner itself, in order to form the uneven shaped surface, the toner cannot be flattened to enhance roughness, and fixing property deteriorates, and this causes falling of the toner. On the contrary, in order to prevent the falling of the toner, there are problems such as when the fixing property is increased, roughness decreases, and it is difficult to obtain compatible condition.
In the proposal of the JP-A No.10-123863, there are problems such as in comparison with transparent toner particle size, considerably small size fine particle is blended, the uneven shaped surface remains in a minor range and the effect is small, and in the case of changing the uneven shape, it is necessary to change the toner itself, cannot be dealt flexibly with.
In the proposal of the JP-A No. 2001-305816, there are problems such as subtle control of fixing condition (toner thickness and viscosity), lacking in reproducibility, and a limit in controllable surface embodiment.
Thus, in the above-mentioned related arts, the present situation is only unified surface treatment is possible and there is no general versatility as a system, and in the point of operating efficiency and operating property, there is no art comprising sufficient satisfactory property, and further improvement and development are desired.
SUMMARY OF THE INVENTIONThe object of the present invention is to provide a surface treating material and a surface treating process using the surface treating material capable of giving simply and effectively desired surface property on a surface of an image recording layer of an image recording material after image recording.
The surface treating material of the present invention comprises a fusible particle and hardly fusible particle which are used for changing a surface property on a surface of an image recording layer of an image recording material after image recording, wherein the fusible particle is melted to form a continuous film by a surface treatment, and a flow starting temperature of the fusible fine particle is 50° C. or more, and less than a heating temperature in the surface treatment, and wherein the hardly fusible particle is not melted with maintaining a particle shape by the surface treatment, and a volume average particle diameter of the hardly fusible particle is 1 μm to 30 μm. The surface treating material of the present invention is capable of giving simply and effectively desired surface property on a surface of an image recording layer of an image recording material after image recording selected from any one of a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
The surface treating process of the present invention, in a first embodiment, on a surface of an image recording layer of an image recording material after image recording, comprises adhering a surface treating material of the present invention, and forming a surface treating layer where the hardly fusible particle is dispersed in a continuous film by melting fusible particle by a heating and pressurizing treatment.
The surface treating process of the present invention, in a second embodiment, comprises forming a laminated body by putting together a surface layer and an image recording layer of the image recording material after image recording by heating and pressurizing treatment, forming a surface treating layer by cooling and separating the laminated body from a base, and the surface layer comprising a fusible particle and hardly fusible particle are deposed on a base, the surface layer changes a surface property of the image recording layer of the image recording material after image recording, wherein the fusible particle is melted to form a continuous film by a surface treatment, and a flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment, and the hardly fusible particle is not melted with maintaining a particle shape by the surface treatment, and a volume average particle diameter is 1 μm to 30 μm, and the a surface treating layer comprises the hardly fusible particle is dispersed in the continuous film which is formed by melting the fusible particle.
The surface treating process in the first and second embodiment of the present invention is capable of giving simply and effectively desired surface property on the surface of the image recording layer of the image recording material selected from at least any one of an electrophotographic image-receiving sheet, a melting heat-transfer recording sheet, a sublimation heat-transfer recording sheet, a heat-sensitive recording sheet and an ink jet recording sheet.
In the present invention, the hardly fusible particle represents particle which has a flow starting temperature (or melting point) is higher than the fusible particle, is able to maintaining a particle shape far from melting during the surface treatment after image recording, and specifically, does not melt at 130° C. or less. The maintaining a particle shape also includes slightly changed particle shape.
BRIEF DESCRIPTION OF THE DRAWINGS
(Surface Treating Material)
The surface treating material of the present invention, in a first embodiment, comprises a fusible particle and a hardly fusible particle, and further comprises other components, if necessary.
The surface treating material of the present invention, in a second embodiment, comprises a base, and at least a surface layer comprising a fusible particle and a hardly fusible particle on the base, and further comprises other layers, if necessary.
The surface treating material of the present invention is used for changing surface property on a surface of an image recording layer of an image recording material after image recording. The Surface property can be suitably controlled by forming a sea-island structure where the hardly fusible particle is dispersed in a continuous film formed after surface treatment.
The surface property is preferably changed at least a part of the surface of the image recording layer, and may be the entire surface of the image recording layer.
The surface property may be preferably selected from any one of a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
The surface property is preferably capable of changing depending on the selection by a user.
A user selection means can be (1) a method assigning image data displayed on a monitor with a mouse, (2) a method inputting with a keyboard, and (3) a method pressing a monitor screen with a finger.
According to the present invention, the surface property is changed by changing any one of a total adhesion amount of the surface treating material corresponding to image information, a combination of the hardly fusible particle and fusible particle, and a mixing ratio of the hardly fusible particle and fusible particle.
Here, the image information may be at least one selected from an image brightness, an image density, an image tone, an image size and a combination thereof. For example, gloss can be given to a part of a background of a sheet body. As high brightness part becomes bright and dark part becomes matte by distributing the gloss a three-dimensional effect can be given to the image.
The image recording material is not limited, and may be suitably selected according to the purpose, for example, an electrophotographic image-receiving sheet, a melting heat-transfer recording sheet, a sublimation-heat-transfer recording sheet, a heat-sensitive recording sheet and an ink jet recording sheet.
The electrophotographic image-receiving sheet, for example, comprises a support, and at least a toner image-receiving layer on the support, and the toner image-receiving layer accepts at least one of a color toner and black toner, and on which image is formed.
The electrophotographic image-receiving sheet is described in detail.
[Support]
The support is not limited, and may be suitably selected according to the purpose, for example, a raw paper, a synthetic paper, a synthetic resin sheet, a coated paper, and a laminated paper. The support can be a single layer composition, or a laminated structure of 2 layers or more. Among them, laminated paper comprising polyolefin resin layer on both surfaces of a raw paper is preferable because of smooth gloss property and stretching property.
—Raw paper—
The raw paper is not limited, and may be suitably selected according to the purpose, specifically, a fine paper, for example, the paper reported in 223 to 224 pages of “The Basic of Photographic Engineering-Silver Salt Photograph Volume” (edited by The Society of Photographic Science and Technology of Japan, Corona Corporation) (issued 1979) is suitable.
The raw paper, used for a support is not limited as long as it is a well-known material and may be suitably selected from various materials according to the purpose, for example, natural pulp of conifer and broadleaf tree, and a mixture of the natural pulp and synthetic pulp, are suitable.
The pulp that can be used as the material of the raw paper is desirable to be bleached broadleaf tree kraft pulp (LBKP), but bleached conifer kraft pulp (NBKP) and broadleaf tree sulfite pulp (LBSP) can also be used because they enhance the surface smoothness, stiffness and dimension stability (curl property) of the raw paper at the same time with good balance and to sufficient level.
As the beating of the pulp, a beater and a refiner can be used.
The Canada Standard Filtered Water Degree of the pulp is preferably 200 ml to 440 ml C.S.F., and more preferably 250 ml to 380 ml C.S.F. because in the paper making step, the shrinkage of the paper can be controlled.
Various additives, for example, fillers, dry paper reinforcers, sizing agents, wet paper reinforcers, fixing agents, pH regulators or other agents, or the like may be added, if necessary, to the pulp slurry (hereafter, may be referred to as pulp paper material) which is obtained after beating the pulp.
Examples of the fillers include calcium carbonate, clay, kaolin, China clay, talc, titanium oxide, diatomite, barium sulfate, aluminum hydroxide, and magnesium hydroxide, and the like. Examples of the dry paper reinforcers cationized starch, cationized polyacrylamide, anionized polyacrylamide, ampholytic polyacrylamide, and carboxy-modified polyvinyl alcohol, and the like.
Examples of the sizing agents include compound comprises higher fatty acid such as higher fatty acid salt; rosin derivatives such as rosin and rosin maleate rosin; paraffin wax, alkylketene dimer, alkenyl succinic anhydride (ASA); and epoxidized fatty amide, and the like.
Examples of the wet paper reinforcers include polyamine polyamide epichlorohydrin, melamine resin, urea resin, and epoxidized polyamide resin, and the like. Examples of the fixing agents include polyvalent metal salt such as aluminum sulfate and aluminum chloride; cationic polymer such as cationized starch, and the like.
Examples of the pH regulators include caustic soda and sodium carbonate. Examples of other agents include defoaming agents, dyes, slime control agents, fluorescent whitening agents, and the like.
Further, flexibilizer can be added if necessary. The flexibilizer, for example, may be the one described in “New Paper Processing Handbook”, pp. 554 to 555, (edited by Kamiyaku Time Corporation) (issued 1980).
These various additives may be used alone or in combination. Also, the amount of these various additives to be added to the pulp paper material is not limited and may be suitably selected according to the purpose, generally, preferably 0.1% by mass to 1.0% by mass.
For the pulp slurry, further, according to necessity, pulp paper material comprising the above-mentioned various additives is paper-made using paper machine such as a hand paper machine, a wire paper machine, a cylinder paper machine, a twin wire machine and a combination machine, and after that dried, and a raw paper is made. Also, according to desire, the surface size treatment can be carried out any one of before and after the drying.
The treatment solution used for sizing a surface is not limited and may be suitably selected according to the purpose, for example, may comprise a water-soluble polymer compound, a water-resistant substance, a pigment, a dye and a fluorescent whitening agent, and the like.
The water-soluble polymer compound, for example, may be cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, polyacrylic sodium, styrene-maleic anhydride copolymer sodium salt and polystyrene sulfonic acid sodium salt, and the like.
The water-resistant substance, for example, may be latex emulsion such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene and vinylidene chloride copolymer, and polyamide-polyamine-epichlorohydrin, and the like.
The pigment, for example, may be calcium carbonate, clay, kaolin, talc, barium sulfate and titanium oxide, and the like.
For the raw paper, in an attempt to improve the rigidity and dimensional stability (curl properties), the ratio (Ea/Eb) of vertical direction Young's modulus (Ea) and horizontal direction Young's modulus Eb is preferably in the range of 1.5 to 2.0. In the range of the value of Ea/Eb is less than 1.5, or more than 2.0, it is not preferable because the rigidity and the curl properties of the recording material is likely to be inferior, and may interfere with paper during the conveying operation.
Generally, it is understood that the “stiffness” of the paper differs depending on the various manners in which the paper is beaten, and after beating, the elastic force (rate) of the paper produced by paper making can be used as an important factor to show the degree of “stiffness” of the paper. By making use of the relation of the dynamic elastic modulus and density showing the properties of viscoelastic material of the paper, and using the ultrasonic vibrating element to this, and measuring the sound velocity transmitting all over the paper, the elastic modulus of the paper can be seek according to the following equation in particular.
E=ρc2(1−n2)
provided that, in the above equation, “E” implies dynamic elastic modulus. “ρ” represents density. “c” represents sound velocity all over the paper. “n” represents Poisson's ratio.
Also, in the case of ordinary paper, as n=0.2 approximately, there is no great difference even by calculating with the following equation, and can be calculated.
E=ρc2
Namely, if the density and sound velocity of the paper can be measured, elastic modulus can be easily found. In the above equation, when measuring sound velocity, various well-known apparatuses such as Sonic Tester-SST-110 (manufactured by Nomura Shoji Co., Ltd.) may be used.
For the raw paper, in order to give desired center line average roughness on the surface, for example, as reported in Japanese Patent Application Laid-Open (JP-A) No.58-68037, it is preferable to use pulp fiber of fiber length distribution (for example the total of 24 mesh screen residue and 42 mesh screen residue, for example, is 20% by mass to 45% by mass, and 24 mesh screen residue is 5% by mass or less. Also, the center line average roughness can be adjusted by adding heating and pressuring to a surface of the raw paper, with a machine calender and super calender, and the like.
The thickness of the raw paper is not limited and may be suitably selected according to the purpose, generally, preferably 30 μm to 500 μm, more preferably 50 μm to 300 μm, and still more preferably 100 μm to 250 μm. The basis weight of the raw paper is not limited and may be suitably selected according to the purpose, for example, preferably 50 g/m2 to 250 g/m2, and more preferably 100 g/m2 to 200 g/m2.
—Synthetic Paper—
The synthetic paper is a paper with polymer fiber except cellulose as a main component, and the polymer fiber, for example, may be polyolefin fiber such as polyethylene and polypropylene, and the like.
—Synthetic Resin Sheet (Film)—
The synthetic resin sheet (film) may be a film formed in a sheet shape from synthetic resin, for example, polypropylene film, stretched polyethylene film, stretched polypropylene film, polyester film, stretched polyester film, and nylon film, and the like. According to stretching, white color film comprising white-colored film and white color pigment, may also be used.
—Coated Paper—
The coated paper is a paper where various resins are coated on one surface or both surfaces on a substrate of a raw paper, and the coating amount differs according to the application. Examples of the coated paper include an art paper, a cast coat paper, and a Yankee paper, and the like.
The resin is coated on the surface of the raw paper is not limited and may be suitably selected according to the purpose, however thermoplastic resin is suitable. The thermoplastic resin can be (1) polyolefin resin (2) polystyrene resin, (3) acrylic resin, (4) poly vinyl acetate or its derivatives, (5) polyamide resin, (6) polyester resin, (7) polycarbonate resin, (8) polyether resin (or acetal resin), and (9) other resins. These thermoplastic resins may be used alone, or in combination.
—Laminated Paper—
The laminated paper is a paper may be formed by laminating various resins, such as rubber or polymer sheets or films, which may be referred to as laminating materials, on a substrate of a raw paper. Examples of the laminating materials include polyolefin resin, polyvinyl chloride resin, polyester resin, polystyrene resin, polymethacrylate resin, polycarbonate resin, polyamide resin, and triacetyl cellulose, and the like. These resins may be used alone, or in combination.
The polyolefin resin, generally, is often formed by using low density polyethylene resin, however, in order to increase the heat resistance of the support, it is preferable to use polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, and a blend of high density polyethylene and low density polyethylene. From the point of cost and laminated properties, using the blend of high density polyethylene and low density polyethylene is the most preferable in particular.
The mixing ratio (mass ratio) of the high density polyethylene and the low density polyethylene is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and still more preferably 3/7 to 7/3. When thermoplastic resin layers are forming on both surfaces of the raw paper, the back surface of the raw paper, for example, is preferably formed by using high density polyethylene, or a blend of high density polyethylene and the low density polyethylene. The molecular mass of the polyethylene is not limited, however, the melt index for any one of the high density polyethylene and low density polyethylene is preferably between 1.0 g/10 min to 40 g/10 min, and comprises extrusion suitability.
Treatment giving white light reflecting property can be performed on these sheets or films. Treatment method like this, for example, can be a method adding pigment such as titanium oxide into these sheets or films.
The thickness of the support is preferably 25 μm to 300 μm, and more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm.
[Toner Image-Receiving Layer]
The toner image-receiving layer, from the point of giving a near-photographic feel to the electrophotographic image-receiving sheet, is preferably a low transparency toner image-receiving layer having a light transmittance of 78% or less, and more preferably the light transmittance is 73% or less, and still more preferably 72% or less.
The light transmittance may be measured by forming a coating layer with the same thickness on a separate polyethylene terephthalate film (thickness 100 μm) and for the coating layer, using direct reading hazemeter (Suga Testing Machine HGM-2DP).
The toner image-receiving layer comprises at least a thermoplastic resin, and according to necessity, comprises various additives which are added in order to improve thermodynamic properties of a toner image-receiving layer, for example, a releasing agent, a plasticizer, a colorant, a filler, a crosslinking agent, a charge control agent, an emulsifying agent, and a dispersing agent.
—Thermoplastic Resin—
The thermoplastic resin is not limited and may be suitably selected according to the purpose, may be (1) polyolefin resin (2) polystyrene resin, (3) acrylic resin, (4) poly vinyl acetate or its derivatives, (5) polyamide resin, (6) polyester resin, (7) polycarbonate resin, (8) polyether resin (or acetal resin), and (9) other resins. These can be used alone, or two or more may be used in combination. Among them, because of toner imbedding, high cohesive energy styrene resin, acrylic resin, and polyester resin are suitably used in particular.
The (1) polyolefin resin, for example, may be polyolefin resins such as polyethylene and polypropylene, and copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, and the like. The copolymer resin of olefin and other vinyl monomers, for example, may be ethylene-vinyl acetate copolymer and ionomer resin, copolymer of acrylic acid and methacrylic acid. The derivatives of polyolefin resin may be chlorinated polyethylene and chlorosulfonated polyethylene, and the like.
The (2) polystyrene resin, for example, may be polystyrene resin, styrene-isobutylene copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and polystyrene-maleic anhydride resin, and the like.
The (3) acrylic resin, for example, may be polyacrylic acid or its esters, polymethacrylic acid or its esters, polyacrylonitrile, and polyacrylamide, and the like.
The polyacrylic acid esters may be homopolymer and plural copolymer of esters of acrylic acid, and the like. The acrylic acid esters, for example, may be methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-ethyl chloride acrylate, phenyl acrylate, and α-chloromethyl acrylate, and the like.
The polymethacrylic acid esters, for example, may be homopolymer and plural copolymer of esters of methacrylic acid. The methacrylic acid esters, for example, may be methyl methacrylate, ethyl methacrylate, butyl methacrylate.
The (4) poly vinyl acetate or its derivatives, for example, may be poly vinyl acetate, polyvinyl alcohol obtained by saponificating poly vinyl acetate, and polyvinyl acetal resin obtained by reacting polyvinyl alcohol with aldehyde (for example, formaldehyde, acetaldehyde, and butyraldehyde).
The (5) polyamide resin is a polycondensation products of diamine and dihydric acid, and may be nylon 6 and nylon 66.
The (6) polyester resin is a polycondensation products of of an acid component and an alcohol component. The acid component is not limited and may be suitably selected according to the purpose, for example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic asid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, trimellitic acid, pyromellitic acid, and anhydride thereof or lower alkyl ester thereof, and the like.
The alcohol component is not limited and may be suitably selected according to the purpose, for example, dihydroxy alcohol is preferable. Aliphatic diol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The alkylene oxide additive of bisphenol A, for example, may be polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane, and polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, and the like.
The (7) polycarbonate resin is generally polycarbonate from bisphenol A and phosgene.
The (8) polyether resin (or acetal resin), for example, may be polyether resin such as polyethylene oxide and polypropylene oxide, and acetal resin such as polyoxymethylene obtained through ring-opening-polymerization, and the like.
The (9) other resins may be polyurethane resin obtained through additional-polymerization.
The thermoplastic resin preferably satisfies toner image-receiving layer properties, which will be described later, when formed into a toner image-receiving layer, and more preferably satisfies the toner image-receiving layer properties by itself. It is also preferable to use in combination two or more resins which have different toner image-receiving layer properties.
The thermoplastic resin preferably has a molecular mass that is larger than that of a thermoplastic resin used in the toner. However, according to the relationship of the thermodynamic properties of the thermoplastic resin used in the toner and the properties of the resin used in the toner image-receiving layer, the relationship of the molecular mass as described above is not necessarily preferable. For example, when a softening temperature of the resin used in the toner image-receiving layer is higher than that of the thermoplastic resin used in the toner, there are cases in which molecular mass of the resin used in the toner image-receiving layer is preferably the same or smaller.
It is also preferred that the thermoplastic resin be a mixture of resins with identical compositions having different average molecular mass. The preferable relationship with molecular mass of thermoplastic resins used in toners is disclosed in JP-A No. 08-334915.
Molecular mass distribution of the thermoplastic resin is preferably wider than that of the thermoplastic resin used in the toner.
It is preferred that the thermoplastic resin satisfies the physical properties disclosed in Japanese Patent Application Laid-Open (JP-A) Nos. 05-127413, 08-194394, 08-334915, 08-334916, 09-171265, and 10-221877.
For the thermoplastic resin for toner image-receiving layer, (i) there is no discharge of organic solvent in the coating and drying, and excels in environment suitability and operation suitability, (ii) the releasing agent such as wax often difficult to dissolve in a solvent at room temperature, often it is dispersed in a solvent (water, organic solvent) before use. Further, an aqueous dispersion is more stable and is excellently suitable for a manufacturing process. In addition, with aqueous coating, wax bleeds on the surface more easily during the process of coating and drying, and the effects of a release agent (offset resistance, adhesion resistance, and the like) is facilitated more easily. Thus, aqueous resins such as aqueous polymer, water-dispersible polymer are suitably used.
The aqueous resin, as long as it is any one of water-dispersible polymer and aqueous polymer, the composition, bonding structure, molecular structure, molecular mass, molecular mass distribution, and embodiment are not limited and may be properly selected depending on the application. Examples of substituting groups which render a polymer aqueous include sulfonic acid group, hydroxy group, carboxylic acid group, amino group, amide group, and ether group.
The water-dispersible polymer, for example, maybe properly selected from the group of resin, emulsion, copolymer thereof, mixture, and cation-modified compound where the (1) to (9) thermoplastic resins are water-dispersed, and may be used in combination.
The water-dispersible polymer may be suitably synthesized or commercially available ones. The commercially available ones, for example, as water-dispersed polyester polymer, may be Vylonal series manufactured by Toyobo Co., Ltd., Pesredine A series manufactured by Takamatsu Oil&Fat Co., Ltd., Tuftone UE series manufactured by Kao Corporation, Polyester WR series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and Elleair series manufactured by Unitika Ltd. As water-dispersible acryl polymer, may be Hiross XE, KE, PE series manufactured by Seiko Chemical Industry Corporation, and Jurymer ET series manufactured by Nihon Junyaku Co., Ltd.
The water-dispersible emulsion is not limited and may be properly selected depending on the application, for example, water-dispersible polyurethane emulsion, water-dispersible polyester emulsion, chloroprene emulsion, styrene-butadiene emulsion, nitrile-butadiene emulsion, butadiene emulsion, vinyl chloride emulsion, vinylpyridine-styrene-butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion, ethylene- vinyl acetate emulsion, vinylidene chloride emulsion, and methyl methacrylate-butadiene emulsion, and the like. Among them, water-dispersible polyester emulsion is preferable in particular.
The water-dispersible polyester emulsion is preferably self-dispersing aqueous polyester emulsion, and among them, carboxyl group comprised self-dispersing aqueous polyester resin emulsion is preferable in particular. The self-dispersing aqueous polyester emulsion represents aqueous emulsion comprising polyester resin able to self-dispersing in aqueous solvent without using emulsifying agent. The carboxyl group comprised self-dispersing aqueous polyester resin emulsion represents aqueous emulsion comprising carboxyl group as a hydrophilic group, and comprising polyester resin able to self-dispersing in aqueous solvent.
The self-dispersing water-dispersible polyester emulsion is preferably satisfying the following (1) to (4) properties. As this is a self-dispersing type which does not use a surfactant, its hygroscopicity is low even in a high humidity environment, its softening point is not much reduced by moisture, and offset produced during fixing, or sticking of sheets in storage, can be suppressed. Moreover, since it is aqueous, it is very environment-friendly and has excellent workability. As it uses a polyester resin which easily assumes a molecular structure with high cohesion energy, it has sufficient hardness in a storage environment, assumes a melting state of low elasticity (low viscosity) in the fixing step for electrophotography, and toner is embedded in the toner image-receiving layer so that a sufficiently high image quality is attained.
(1) Number average molecular mass (Mn) is preferably 5,000 to 10,000, and more preferably 5,000 to 7,000.
(2) Molecular mass distribution (mass average molecular mass/number average molecular mass) is preferably 4 or less, and Mw/Mn□3 is more preferably.
(3) Glass transition temperature (Tg) is preferably 40° C. to 100° C., and more preferably 50° C. to 80° C.
(4) Volume average particle diameter is preferably 20 nm to 200 nm, and more preferably 40 nm to 150 nm.
The amount of the water-dispersible emulsion in the toner image-receiving layer is preferably 10% by mass to 90% by mass, and more preferably 10% by mass to 70% by mass.
The water-soluble polymer is not limited and may be properly selected depending on the application, and suitably synthesized or commercially available ones may be used, for example, polyvinyl alcohol, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, polyethylene oxide, gelatin, cationized starch, casein, polyacrylic sodium, styrene-maleic anhydride copolymer sodium salt and polystyrene sulfonic acid sodium salt, and the like. Among them, polyethylene oxide is preferable.
The commercially available water-soluble polymer may be, as water-soluble polyester, various plas coat manufactured by Goo Chemical Co., Ltd., Finetex ES series manufactured by Dainippon Ink And Chemicals, Inc., as water-soluble acryl, Jurymer AT series manufactured Nihon by Junyaku Co., Ltd., Finetex 6161, K-96 manufactured by Dainippon Ink And Chemicals, Inc.; Hiross NL-1189, and BH-997L manufactured by Seiko Chemical Industry Corporation.
The water-soluble polymer may be those described in Research Disclosure 17, pp. 26 of No. 643, Research Disclosure 18, pp. 651 of No. 716, Research Disclosure 307, pp. 873 to 874 of No. 105, and Japanese Patent Application Laid-Open (JP-A) No. 64-13546.
The amount of the water-soluble polymer in the toner image-receiving layer is not limited and may be properly selected depending on the application, and it is preferably 0.5 g/m2 to 2 g/m2.
The thermoplastic resin may be used together with other polymer materials, however, in this case, generally the amount is used more than other polymer materials.
The amount of the thermoplastic resin for toner image-receiving layer in the toner image-receiving layer is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and preferably 50% by mass to 90% by mass in particular.
—Releasing Agent—
The releasing agent is blended in the toner image-receiving layer for preventing the offset of the toner image-receiving layer. The releasing agents used in the present invention are not limited and may be properly selected depending on the application so long as it is able to form a layer of the releasing agent on a surface of the toner image-receiving layer by being heated and melted so as to deposit and to remain on the surface of the toner image-receiving layer, and by being cooled and solidified so as to form a layer of the releasing agent, thereafter.
Examples of the releasing agents include at least one selected from silicone compounds, fluorine compounds, waxes and matting agents (i.e., the above-noted particles according to the present invention).
Examples of the releasing agent include also the compounds described in the literatures “Properties and Applications of Waxes, Revised Edition” (published by Saiwai Shobo) and “The Silicon Handbook” (published by THE NIKKAN KOGYO SHIMBUN). Further, preferred examples of the releasing agent include silicon compounds, fluorine compounds and waxes which are used for producing toners which are described in the following patent documents: Japanese Patent Application Publication (JP-B) Nos. 59-38581, 04-32380, Japanese Patent (JP-B) Nos. 2838498 and 2949558, JP-A Nos. 50-117433, 52-52640, 57-148755, 61-62056, 61-62057, 61-118760, 0242451, 0341465, 04-212175, 04-214570, 04-263267, 05-34966, 05-119514, 06-59502, 06-161150, 06-175396, 06-219040, 06-230600, 06-295093, 07-36210, 0743940, 07-56387, 07-56390, 07-64335, 07-199681, 07-223362, 07-287413, 08-184992, 08-227180, 08-248671, 08-248799, 08-248801, 08-278663, 09-152739, 09-160278, 09-185181, 09-319139, 09-319143, 10-20549, 1048889, 10-198069, 10-207116, 11-2917, 1144969, 11-65156, 11-73049 and 11-194542. These compounds may be used in combination.
Examples of the silicone compounds include silicone oils, silicone rubbers, silicone particles, silicone-modified resins and reactive silicone compounds, and the like.
Examples of the silicone oils include unmodified silicon oil, amino-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, vinyl-modified silicone oil, epoxy-modified silicone oil, polyether-modified silicone oil, silanol-modified silicone oil, methacryl-modified silicone oil, mercapto-modified silicone oil, alcohol-modified silicone oil, alkyl-modified silicone oil and fluorine-modified silicone oil, and the like.
Examples of the silicone-modified resins include silicone-modified resins produced by silicone-modifying resins, such as an olefinic resin, a polyester resin, a vinyl resin, a polyamide resin, a cellulose resin, a phenoxy resin, a vinyl chloride-vinyl acetate resin, an urethane resin, an acrylic resin, a styrene-acrylic resin or a silicone-modified resin produced by a copolymer resin thereof, and the like.
The fluorine compounds are not limited and may be properly selected depending on the application. Examples of the fluorine compounds include fluorocarbon oil, fluorocarbon rubber, fluorine-modified resin, fluorosulfonic acid compound, fluorosulfonic acid, fluoric acid compound and salts thereof and inorganic fluoride, and the like.
The wax is generally classified into a natural wax and a synthesized wax.
Preferred examples of the natural wax include vegetable wax, animal wax, mineral wax and petroleum wax, and the like. Among them, the vegetable wax is most preferred. As the natural wax is preferably a water-dispersible wax particularly from the viewpoint of the compatibility when a aqueous resin is used as the polymer in the toner image-receiving layer.
The vegetable wax is not limited and may be properly selected from conventional vegetable waxes which may be properly synthesized or commercially available. Examples of the vegetable wax include carnauba wax, castor oil, rape oil, soy bean oil, Japan tallow, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax and jojoba oil, and the like.
Examples of the carnauba wax which is commercially available include EMUSTAR-0413 (manufactured by Nippon Seiro Co., Ltd.) and SELOSOL 524 (manufactured by Chukyo Yushi Co., Ltd.). Examples of the castor oil which is commercially available include purified castor oil (manufactured by Itoh Oil Chemicals Co., Ltd).
Among them, the carnauba wax having a melting point of from 70° C. to 95° C. is most preferable from the viewpoint of providing an electrophotographic image-receiving sheet which is excellent particularly in anti-offset properties, adhesion resistance, conveyability and gloss, is less likely to cause crack and splitting, and is capable of forming a high quality image.
The animal wax is not limited and may be properly selected from conventional animal waxes. Examples of the animal wax include bees wax, lanolin, spermaceti wax, whale oil and wool wax, and the like.
The mineral wax is not limited and may be properly selected form conventional mineral waxes which may be commercially available or properly synthesized. Examples of the mineral wax include montan wax, montan ester wax, ozokerite and ceresin.
Among them, particularly from the viewpoint of providing an electrophotographic image-receiving sheet which is excellent particularly in anti-offset properties, adhesion resistance, conveyability and gloss, and in which the crazing is hardly caused and an image having a high quality can be formed, the montan wax having a melting point of from 70° C. to 95° C. is most preferred.
The petroleum wax is not limited and may be properly selected conventional petroleum waxes which may be commercially available or properly synthesized. Examples of the petroleum wax include paraffin wax, microcrystalline wax and petrolatum, and the like.
The amount of the natural wax in the toner image-receiving layer is preferably from 0.1 g/m2to 4 g/m2, more preferably from 0.2 g/m2to 2 g/m2.
When the amount is less than 0.1 g/m2, the anti-offset properties and the adhesion resistance of the image-receiving sheet may be particularly impaired. On the other hand, when the amount is more than 4 g/m2, the quality of the image formed on the image-receiving sheet may be impaired due to excessive wax.
The melting point of the natural wax is, particularly from the viewpoint of the anti-offset properties and the conveyability, preferably from 70° C. to 95° C., more preferably from 75° C. to 90° C.
The synthetic wax is classified into a synthetic hydrocarbon, a modified wax, a hydrogenated wax and other synthetic waxes produced from fats and oils. As the wax, from the viewpoint of the compatibility of the wax with a hydrophilic thermoplastic resin used as a thermoplastic resin for producing the toner image-receiving layer, a water-dispersible wax is preferred.
Examples of the synthetic hydrocarbon include a Fischer-Tropsch wax and a polyethylene wax.
Examples of the synthetic wax produced from fats and oils include an acid amide such as stearamide and an acid imide such as anhydrous phthalimide, and the like.
The modified wax is not limited and may be properly selected depending on the application. Examples of the modified wax include an amine-modified wax, an acrylic acid-modified wax, a fluorine-modified wax, an olefin-modified wax, a urethane wax and an alcohol wax, and the like.
The hydrogenated wax is not limited and may be properly selected depending on the application. Examples of the hydrogenated wax include hard castor oil, castor oil derivative, stearic acid, lauric acid, myristic acid, palmitic acid, behenic acid, sebacic acid, undecylenic acid, heptyl acid, maleic acid and a highly maleinated oil, and the like.
The melting point of the releasing agent is, particularly from the viewpoint of the anti-offset properties and the conveyability of the image-receiving sheet, preferably from 70° C. to 95° C., more preferably from 75° C. to 90° C.
As the releasing agent incorporated in the composition of the toner image-receiving layer of the present invention, a derivative, an oxide, a refined product and a mixture of the above-exemplified releasing agents may be also used.
These releasing agents may have a reactive substituent.
The amount of the releasing agent in the toner image-receiving layer is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 8.0% by mass, still more preferably 1% by mass to 5.0% by mass.
—Plasticizer—
The plasticizer is not limited and may be properly selected from conventional plasticizers used for the resin depending on the application. The plasticizer has the function to control the fluidizing and softening of the toner image-receiving layer by the heat and pressure applied on the toner image-receiving layer during fixing of the toner.
Examples of a reference for selecting the plasticizer include literatures, such as “Kagaku Binran“(Chemical Handbook) (edited by The Chemical Society of Japan and published by Maruzen Co., Ltd.), “Plasticizer, Theory and Application” (edited by Koichi Murai and published by Saiwai Shobo), “Volumes 1 and 2 of Studies on Plasticizer” (edited by Polymer Chemistry Association) and “Handbook on Compounding Ingredients for Rubbers and Plastics” (edited by Rubber Digest Co.).
Some plasticizers are described as an organic solvent having a high boiling point or a heat solvent in some literatures. Examples of the plasticizer include compound such as esters such as phthalate esters, phosphorate esters, fatty esters, abietate esters, adipate esters, sebacate esters, azelate esters, benzoate esters, butyrate esters, epoxidized fatty esters, glycolate esters, propionate esters, trimellitate esters, citrate esters, sulfonate esters, carboxylate esters, succinate esters, malate esters, fumarate esters, phthalate esters and stearate esters; amides such as fatty amides and sulfonate amides; ethers; alcohols; lactones and polyethylene oxides, which are described in patent documents, such as JP-A Nos. 59-83154, 59-178451, 59-178453, 59-178454, 59-178455, 59-178457, 62-174754, 62-245253, 61-209444, 61-200538, 62-8145, 62-9348, 62-30247, 62-136646, and 2-235694.
These plasticizers may be incorporated in the composition of the resin.
Further, a plasticizer having a relatively low molecular mass can be also used. The plasticizer has a molecular mass which is preferably lower than that of a binder resin which is plasticized by the plasticizer and preferably 15,000 or less, more preferably 5,000 or less. In addition, when a plasticizer is a polymer, the plasticizer is preferably the same polymer as that of the binder resin which is plasticized by the plasticizer. For example, for plasticizing a polyester resin, the plasticizer is preferably a polyester having a low molecular mass. Further, an oligomer can be also used as a plasticizer.
Besides the above-noted compounds, examples of the plasticizer which is commercially available include Adekacizer PN-170 and PN-1430 (manufactured by Asahi Denka Kogyo Co., Ltd.); PARAPLEX G-25, G-30 and G-40 (manufactured by C. P. Hall Co., Ltd.); and Ester Gum 8L-JA, Ester R-95, Pentalin 4851, FK 115, 4820, 830, Luisol 28-JA, Picolastic A75, Picotex LC and Crystalex 3085 (manufactured by Rika Hercules Co., Ltd.).
The plasticizer may be optionally used for relaxing the stress and strain (i.e., a physical strain, such as a strain in elastic force and viscosity and a strain due to a material balance in the molecule and the backbone chain and pendant moiety of the binder) which are caused when the toner particles are embedded in the toner image-receiving layer.
In the toner image-receiving layer, the plasticizer may be finely (microscopically) dispersed, may be in the state of a fine phase-separation in a sea-island structure and may be compatibilized with other components, such as a binder resin.
The amount of the plasticizer in the toner image-receiving layer is preferably 0.001% by mass to 90% by mass, more preferably 0.1% by mass to 60% by mass, still more preferably 1% by mass to 40% by mass, based on the mass of the toner image-receiving layer.
The plasticizer may be used for controlling slip properties (for improving the conveyability by reducing the friction), improving the offset of the toner at the fixing part of the fixing apparatus (peeling of the toner or the toner image-receiving layer to the fixing part) and controlling the curling balance and electrostatic charge (formation of a toner electrostatic image).
—Colorant—
The colorant is not limited and may be properly selected depending on the application. Examples of the colorant include a fluorescent whitening agent, a white pigment, a colored pigment and a dye.
The fluorescent whitening agent is not limited so long as the agent is a conventional compound having an absorption in the near-ultraviolet region and emitting a fluorescence having a wavelength of 400 nm to 500 nm and may be properly selected from conventional fluorescent whitening agents. Preferred examples of the fluorescent whitening agent include the compounds described in the literature “The Chemistry of Synthetic Dyes, Volume V” (edited by K. Veen Rataraman, Chapter 8). The fluorescent whitening agent may be a commercially available product or a properly synthesized product. Examples of the fluorescent whitening agent include stilbene compounds, coumarin compounds, biphenyl compounds, benzo-oxazoline compounds, naphthalimide compounds, pyrazoline compounds and carbostyril compounds. Examples of the commercially available fluorescent whitening agent include white furfar-PSN, PHR, HCS, PCS and B (manufactured by Sumitomo Chemicals Co., Ltd.) and UVITEX-OB (manufactured by Ciba-Geigy Corp.), and the like.
The white pigment is not limited and may be properly selected from conventional white pigments depending on the application. Examples of the white pigment include an inorganic pigment, such as titanium oxide and calcium carbonate, and the like.
The colored pigment is not limited and may be properly selected from conventional colored pigments. Examples of the colored pigment include various pigments described in JP-A No. 6344653, such as an azo pigment, a polycyclic pigment, a condensed polycyclic pigment, a lake pigment and a carbon black, and the like.
Examples of the azo pigment include an azo lake pigment (such as carmine 6B and red 2B), an insoluble azo pigment (such as monoazo yellow, disazo yellow, pyrazolone orange and Vulcan orange) and a condensed azo pigment (such as chromophthal yellow and chromophthal red), and the like.
Examples of the polycyclic pigment include a phthalocyanine pigment, such as copper phthalocyanine blue and copper phthalocyanine green.
Examples of the condensed polycyclic pigment include a dioxazine pigment such as dioxazine violet, an isoindolinone pigment such as isoindolinone yellow, a threne pigment, a perylene pigment, a perinone pigment and a thioindigo pigment, and the like.
Examples of the lake pigment include malachite green, rhodamine B, rhodamine G and Victoria blue B.
Examples of the inorganic pigment include an oxide such as titanium dioxide and iron oxide red, a sulfate salt such as precipitated barium sulfate, a carbonate salt such as precipitated calcium carbonate, a silicate salt such as a hydrous silicate salt and an anhydrous silicate salt, and a metal powder such as aluminum powder, bronze powder, zinc powder, chrome yellow and iron blue, and the like.
These pigments may be used alone or in combination.
The dye is not limited and may be properly selected from conventional dyes depending on the application. Examples of the dye include anthraquinone compounds and azo compounds, and the like. These dyes may be used alone or in combination.
Examples of the water-insoluble dye include a vat dye, a disperse dye and an oil-soluble dye, and the like. Specific examples of the vat dye include C. I. Vat violet 1, C. I. Vat violet 2, C. I. Vat violet 9, C. I. Vat violet 13, C. I. Vat violet 21, C. I. Vat blue 1, C. I. Vat blue 3, C. I. Vat blue 4, C. I. Vat blue 6, C. I. Vat blue 14, C. I. Vat blue 20 and C. I. Vat blue 35. Specific examples of the disperse dye include C. I. disperse violet 1, C. I. disperse violet 4, C. I. disperse violet 10, C. I. disperse blue 3, C. I. disperse blue 7 and C. I. disperse blue 58. Specific examples of the oil-soluble dye include C. I. solvent violet 13, C. I. solvent violet 14, C. I. solvent violet 21, C. I. solvent violet 27, C. I. solvent blue 11, C. I. solvent blue 12, C. I. solvent blue 25 and C. I. solvent blue 55, and the like.
Colored couplers used in the silver halide photography may also be used preferably as the dye.
The amount of the colorant in the toner image-receiving layer is preferably 0.1 g/m2to 8 g/m2, more preferably 0.5 g/m2to 5 g/m2.
When the amount of the colorant is less than 0.1 g/m2, the light transmittance of the toner image-receiving layer may be high. On the other hand, when the amount is more than 8 g/m2, handling properties, such as crack and adhesion resistance may be impaired.
Among the colorants, the additional amount of the pigment is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less based on the mass of the thermoplastic resin which forms the toner image-receiving layer.
Examples of the fillers include an organic filler and an inorganic filler which is a reinforcing agent for the binder resin or a conventional filler as a reinforcer or a bulking agent. The filler may be properly selected by referring to “Handbook of Rubber and Plastics Additives” (edited by Rubber Digest Co.), “Plastics Blending Agents—Basics and Applications” (New Edition) (published by Taisei Co.) and “The Filler Handbook” (published by Taisei Co.).
Examples of the filler include an inorganic filler and an inorganic pigment. Specific examples of the inorganic filler or the inorganic pigment include silica, alumina, titanium dioxide, zinc oxide, zirconium oxide, micaceous iron oxide, white lead, lead oxide, cobalt oxide, strontium chromate, molybdenum pigments, smectite, magnesium oxide, calcium oxide, calcium carbonate and mullite, and the like. Among them, silica and alumina are most preferred. These fillers may be used alone or in combination. It is preferred that the filler has a small particle diameter. When the filler has a large particle diameter, the surface of the toner image-receiving layer is easily roughened.
Examples of the silica include a spherical silica and an amorphous silica. The silica can be synthesized by a dry method, a wet method or an aerogel method. The silica may be also produced by treating the surface of the hydrophobic silica particles with a trimethylsilyl group or silicone. Preferred examples of the silica include a colloidal silica. The silica is preferably porous.
Examples of the alumina include an anhydrous alumina and a hydrated alumina. Examples of the crystallized anhydrous alumina include α-type, β-type, γ-type, δ-type, ξ-type, η-type, θ-type, κ-type, ρ-type and χ-type anhydrous alumina. The hydrated alumina is more preferred than the anhydrous alumina. Examples of the hydrated alumina include a monohydrated alumina and a trihydrate alumina. Examples of the monohydrated alumina include pseudo-boehmite, boehmite and diaspore. Examples of the trihydrated alumina include gibbsite and bayerite. The alumina is preferably porous.
The hydrated alumina can be synthesized by the sol-gel method in which ammonia is added to a solution of an aluminum salt to precipitate alumina or by a method of hydrolyzing an alkali aluminate. The anhydrous alumina can be obtained by heating to dehydrate a hydrated alumina.
The amount of the filler is preferably 5 parts by mass to 2,000 parts by mass, relative to 100 parts by mass (in terms of dry mass) of the binder resin in the toner image-receiving layer.
The crosslinking agent may be incorporated in the resin composition of the toner image-receiving layer for controlling the shelf stability and thermoplasticity of the toner image-receiving layer. Examples of the crosslinking agent include a compound containing in the molecule two or more reactive groups selected from the group consisting of an epoxy group, an isocyanate group, an aldehyde group, an active halogen group, an active methylene group, an acetylene group and other conventional reactive groups.
Examples of the crosslinking agent include also a compound containing in the molecule two or more groups which can form a bond through a hydrogen bond, an ionic bond or a coordination bond.
Specific examples of the crosslinking agent include a compound which is conventional as a coupling agent, a curing agent, a polymerizing agent, a polymerization promoter, a coagulant, a film-forming agent or a film-forming assistant which are used for the resin. Examples of the coupling agent include chlorosilanes, vinylsilanes, epoxisilanes, aminosilanes, alkoxy aluminum chelates, titanate coupling agents and other conventional crosslinking agents described in the literature “Handbook of Rubber and Plastics Additives” (edited by Rubber Digest Co.).
The toner image-receiving layer preferably comprises a charge control agent for controlling the transfer and adhesion of the toner and for preventing the adhesion of the toner image-receiving layer due to the charge.
The charge control agent is not limited and may be properly selected from conventional various charge control agents depending on the application. Examples of the charge control agent include a surfactant, such as a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a non-ionic surfactant; a polymer electrolyte and a conductive metal oxide. Specific examples of the charge control agent include a cationic antistatic agent, such as a quaternary ammonium salt, a polyamine derivative, a cation-modified polymethyl methacrylate, a cation-modified polystyrene; an alkyl phosphate, an anionic antistatic agent, such as an alkyl phosphate and an anionic polymer; and a non-ionic antistatic agent, such as a fatty ester and a polyethylene oxide.
When the toner is negatively charged, the charge control agent in the toner image-receiving layer is preferably a cationic or nonionic charge control agent.
Examples of the conductive metal oxide include ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO and MoO3. These conductive metal oxides may be used alone or in combination. The conductive metal oxide may contain (dope) another different element, for example, ZnO may contain (dope) Al and In; TiO2 may contain (dope) Nb and Ta; and SnO2 may contain (dope) Sb, Nb and a halogen element.
—Other Additives—
The toner image-receiving layer of the present invention may comprise also various additives for improving the stability of the output image or the stability of the toner image-receiving layer itself. Examples of the additive include various conventional antioxidants, anti-aging agents, deterioration inhibitors, ozone-deterioration inhibitors, ultraviolet light absorbers, metal complexes, light stabilizers, antiseptic agents and anti-fungus agents.
The antioxidant is not limited and may be properly selected depending on the application. Examples of the antioxidant include a chroman compound, a coumarin compound, a phenol compound (e.g., a hindered phenol), a hydroquinone derivative, a hindered amine derivative and a spiroindan compound, and the like. With respect to the antioxidant, there is a description in JP-A No. 61-159644.
The anti-aging agent is not limited and may be properly selected depending on the application. Examples of the anti-aging agent include anti-aging agents described in the literature “Handbook of Rubber and Plastics Additives - Revised Second Edition” (published by Rubber Digest Co., 1993, pp. 76-121).
The ultraviolet light absorber is not limited and may be properly selected depending on the application. Examples of the ultraviolet light absorber include a benzotriazol compound (see U.S. Pat. No. 3,533,794), a 4-thiazolidone compound (see U.S. Pat. No. 3,352,681), a benzophenone compound (see JP-A No. 46-2784) and an ultraviolet light absorbing polymer (see JP-A No. 62-260152).
The metal complex is not limited and may be properly selected depending on the application. Proper examples of the metal complex include metal complexes described in patent documents, such as U.S. Pat. Nos. 4,241,155, 4,245,018, and 4,254,195; and JP-A Nos. 61-88256, 62-174741, 63-199248, 01-75568 and 01-74272.
Also, preferred examples of the ultraviolet light absorber or the light stabilizer include ultraviolet light absorbers or light stabilizers described in the literature “Handbook of Rubbers and Plastics Additives—Revised Second Edition” (published by Rubber Digest Co., 1993, pp. 122-137).
The toner image-receiving layer may optionally comprise the above-noted conventional additives for the photography. Examples of the additive for the photography include additives described in the literatures “Journal of Research Disclosure (hereinafter referred to as RD) No. 17643 (December, 1978), No. 18716 (November, 1979) and No. 307105 (November, 1989)”. These additives are specifically noted with respect to the pages of the Journal RD which are to be referred to a table as shown in the following Table 1.
The toner image-receiving layer is disposed on the support by coating the support with the coating liquid containing a thermoplastic resin used for the toner image-receiving layer with a wire coater or the like and drying the coating solution. The Minimum Film Forming Temperature (MFT) of the thermoplastic resin used in the present invention is preferably room temperature or higher during the storage of the image-receiving sheet before the printing and preferably 100° C. or less during the fixing of the toner particles.
The total thickness of the toner image-receiving layer is not limited and may be properly selected depending on the application, for example, is preferably 2 μm or more, more preferably 2 μm to 50 μm, preferably 5 μm to 15 μm in particular. When the thickness is less than 2 μm, shape forming of specific roughness shape becomes difficult.
[Physical Properties of Toner Image-Receiving Layer]
The 180-degree separation strength of the toner image-receiving layer at the temperature for the image-fixing at which the image is fixed on the fixing member is preferably 0.1N/25 mm or less, more preferably 0.041N/25 mm or less. The 180-degree separation strength can be measured according to the method described in JIS K6887 using a surface material of the fixing member.
It is preferred that the toner image-receiving layer has a high degree of whiteness. The whiteness is measured by the method described in JIS P 8123 and is preferably 85% or more. It is preferred that the spectral reflectance of the toner image-receiving layer is 85% or more in the wavelength range of from 440 nm to 640 nm and the difference between the maximum spectral reflectance of the toner image-receiving layer and the minimum spectral reflectance of the toner image-receiving layer in the wavelength range is within 5%. Further, it is more preferred that the spectral reflectance of the toner image-receiving layer is 85% or more in the wavelength range of 400nm to 700 nm and the difference between the maximum spectral reflectance of the toner image-receiving layer and the minimum spectral reflectance of the toner image-receiving layer in the wavelength range is within 5%.
With respect to the whiteness of the toner image-receiving layer, specifically, an L* value is preferably 80 or higher, more preferably 85 or higher, still more preferably 90 or higher in the CIE 1976 (L* a* b*) color space. The color tint of the white color is preferably as neutral as possible and more specifically, with respect to the color tint of the whiteness, the value of (a*)2+(b*)2 is preferably 50 or less, more preferably 18 or less, still more preferably 5 or less in the (L* a* b*) space.
It is preferred that the toner image-receiving layer has high gloss after the image-forming. With respect to the gloss luster of the toner image-receiving layer, the 45-degree gloss luster is preferably 60 or higher, more preferably 75 or higher, still more preferably 90 or higher over the whole range from white where there is no toner, to black where toner is densed at maximum. However, the gloss luster of the toner image-receiving layer is preferably 110 or less. When the gloss luster is more than 110, the image has a metallic luster and such a quality of the image is undesirable.
The gloss luster can be measured according to JIS Z8741.
It is preferred that the toner image-receiving layer has high smoothness after the fixing. With respect to the smoothness of the toner image-receiving layer, the arithmetic average roughness (Ra) is preferably 3 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, over the whole range from white where there is no toner, to black where toner is densed at maximum.
The arithmetic average roughness may be measured, for example, according to the methods described in JIS B0601, B0651 and B0652.
The toner image-receiving layer has preferably one of the physical properties described in the following items (1) to (6), more preferably several of them, most preferably all of them.
(1) The melting temperature (Tm) of the toner image-receiving layer is preferably 30° C. or higher, more preferably a temperature which is higher than Tm of the toner by 20° C., or lower.
(2) The temperature at which the viscosity of the toner image-receiving layer is 1×105 cp is preferably 40° C. or higher, more preferably a temperature which is lower than the temperature at which the viscosity of the toner is 1×105 cp.
(3) The storage elasticity modulus (G′) of the toner image-receiving layer at the temperature for the image-fixing is preferably from 1×102 Pa to 1×105 Pa and the loss elasticity modulus (G″) of the toner image-receiving layer at the temperature for the image-fixing is preferably from 1×102 Pa to 1×105 Pa.
(4) The loss tangent (G″/G′) of the toner image-receiving layer is preferably from 0.01 to 10, wherein the loss tangent is the ratio of the loss elasticity modulus (G″) to the storage elasticity modulus (G′).
(5) The storage elasticity modulus (G′) of the toner image-receiving layer at the fixing temperature differs from the storage elasticity modulus (G′) of the toner at the fixing temperature, preferably by −50 to +2,500.
(6) The inclination angle of the molten toner on the toner image-receiving layer is preferably 50° or less, more preferably 40° or less.
The toner image-receiving layer preferably satisfies the physical properties described in Japanese Patent No. 2788358 and JP-A Nos. 07-248637, 08-305067 and 10-239889.
The surface electrical resistance of the toner image-receiving layer is preferably in the range of from 1×106 Ω/cm2 to 1×1015 Ω/cm2 (under conditions of 25° C. and 65% Relative Humidity).
When the surface electrical resistance is less than 1×106 Ω/cm2, the amount of the toner transferred to the toner image-receiving layer is insufficient, and the density of the obtained toner image may be too low easily. Cn the other hand, when the surface electrical resistance is more than 1×1015 Ω/cm2, more charge than the necessary is generated during the transfer. Therefore, toner is transferred insufficiently, image density is low and static electricity develops causing dust to adhere during handling of the electrophotographic image-receiving sheet, or misfeed, overfeed, discharge marks or toner transfer dropout may occur.
The surface electrical resistance are measured based on JIS K6911. The sample o is left under the condition where the temperature is 20° C. and the humidity is 65% for 8 hours or more and after applying a voltage of 100V to the sample for 1 minute under the same condition as the above-noted condition, the surface electrical resistance of the toner image-receiving layer is measured using a micro-ammeter R8340 (manufactured by Advantest Ltd.).
[Other Layers]
Examples of the other layers which the electrophotographic image-receiving sheet comprises include a surface protective layer, a backing layer, an contact improving layer, an intermediate layer, an undercoat layer, a cushion layer, a charge control (inhibiting) layer, a reflecting layer, a tint-adjusting layer, a storage ability-improving layer, an anti-adhering layer, an anti-curl layer and a smoothing layer, and the like. These layers may be in a single layer structure or a formed of two or more layers.
—Surface Protective Layer—
The surface protective layer may be disposed on the surface of the toner image-receiving layer to protect the surface of the electrophotographic image-receiving sheet, to improve storage ability to improve handling properties, to facilitate writing, and conveyability within an equipment, to confer anti-offset properties, or the like. The surface protective layer may have one layer, or two or more layers. In the surface protective layer, various thermoplastic resins or thermosetting resins may be used as a binder, and are preferably the same types of resins as those of the toner image-receiving layer. However, the thermodynamic properties and electrostatic properties are not necessarily identical to those of the toner image-receiving layer, and may be individually optimized.
The surface protective layer may comprise the various additives described above which can be used for producing the toner image-receiving layer. In particular, in addition to the releasing agents, the surface protective layer may include other additives, for example matting agents or the like. The matting agents may be any of these used in the related art.
From the viewpoint of fixing properties, it is preferred that the outermost surface layer of the electrophotographic image-receiving sheet (which refers to, for example, the surface protective layer, if disposed) has good compatibility with the toner. Specifically, it is preferred that the contact angle with molten toner is for 0° to 40°.
—Backing Layer—
The backing layer in the electrophotographic image-receiving sheet is preferably disposed on a surface of the support, which is the opposite of the surface on which the toner image-receiving layer is disposed, in order to confer back surface output compatibility, and to improve back surface output image quality, curl balance and conveyability within equipment.
There is no particular limitation on the color of the backing layer. However, if the electrophotographic image-receiving sheet of the invention is a double-sided output image-receiving sheet where an image is formed also on the back surface, it is preferred that the backing layer is also white. It is preferred that the whiteness and spectral reflectance are 85% or more, for both the top surface and the back surface.
To improve double-sided output compatibility, the backing layer may have an identical structure to that of the toner image-receiving layer. The backing layer may comprise the above-described various additives. Of these additives, matting agents and charge control agents are particularly suitable. The backing layer may be a single layer, or may have a laminated structure comprising two or more layers.
Further, if releasing oil is used for the fixing roller or the like, to prevent offset during fixing, the backing layer may have oil absorbing properties.
Usually, the thickness of the backing layer is preferably 0.1 μm to 10 μm.
—Contact Improving Layer—
In the electrophotographic image-receiving sheet, it is preferred to dispose a contact improving layer in order to improve the contact between the support and the toner image-receiving layer. The contact improving layer may contain the various additives described above. Among them, crosslinking agents are particularly preferred to be blended in the contact improving layer. Furthermore, to improve accepting properties to toner, it is preferred that the electrophotographic image-receiving sheet further comprises a cushion layer between the contact improving layer and the toner image-receiving layer.
—Intermediate Layer—
An intermediate layer may for example be disposed between the support and the contact improvement layer, between the contact improvement layer and the cushion layer, between the cushion layer and the toner image-receiving layer, or between the toner image-receiving layer and the storage property improvement layer. In the case of the electrophotographic image-receiving sheet comprising the support, the toner image-receiving layer and the intermediate layer, the intermediate layer may of course be disposed for example between the support and the toner image-receiving layer.
The thickness of the electrophotographic image-receiving sheet of the present invention is not limited and may be properly selected depending on the application. The thickness is preferably from 50 μm to 550 μm, more preferably from 100 μm to 350 μm.
<Toner>
In the electrophotographic image-receiving sheet, the toner image-receiving layer receives toners during printing or copying.
The toner contains at least a binder resin and a colorant, but may contain releasing agents and other components, if necessary.
—Binder Resin for Toner—
The binder resin is not limited and may be selected from resins used usually for producing the toner depending on the application. Examples of the binder resin include homo-polymers or copolymers produced by polymerizing or copolymerizing a vinyl monomer or two or more vinyl monomers selected from the group consisting of vinyl monomers, fro example styrenes, such as styrene and parachlorostyrene; vinyl esters, such as vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propioniate, vinyl benzoate and vinyl butyrate; methylene fatty carboxylate esters, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate; vinyl nitriles, such as acrylonitrile, methacrylonitrile and acrylamide; vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; N-vinyl compounds, such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; and vinyl carboxylic acids, such as methacrylic acid, acrylic acid and cinnamic acid. Examples of the binder resin include also various polyesters. The above-noted examples of the binder resin may be used in combination with various waxes.
Among these resins, a resin of the same type as that of the resin used for producing the toner image-receiving layer according to the present invention is preferably used.
—Colorant for Toner—
The colorant used for the toner is not limited and may be properly selected from colorants generally used in the art in the toner depending on the application. Examples of the colorant include various pigments, such as carbon black, chrome yellow, hansa yellow, benzidine yellow, threne yellow, quinoline yellow, Permanent Orange GTR, Pyrazolone orange, vulcan orange, watchung red, permanent red, Brilliant Carmine 3B, Brilliant Carmine 6B, Du Pont Oil Red, Pyrazolone Red, Lithol Red, Rhodamine B lake, Lake Red C, Rose Bengal, aniline blue, ultra marine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate; and various dyes, such as acridine dyes, xanthene dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, dioxazine dyes, thiazine dyes, azomethine dyes, phthalocyanine dyes, aniline black dyes, polymethine dyes, triphenylmethane dyes, diphenylmethane dyes and thiazole dyes.
These colorants may be used alone or in combination.
The amount of the colorant is not limited and may be properly selected depending on the application. The amount is preferably from 2% by mass to 8% by mass, based on the mass of the toner. When the amount of the colorant is less than 2% by mass, the coloring power of the toner may be weakened. On the other hand, when the amount is more than 8% by mass, the transparency of the toner may be impaired.
—Releasing Agent for Toner—
The releasing agent used for the toner is not limited and may be properly selected from releasing agents generally used in the art in the toner depending on the application. Particularly effective examples of the releasing agent include a highly crystalline polyethylene wax having a relatively low molecular mass, a Fischer-Tropsch wax, amide wax and a polar wax containing nitrogen, such as a compound having a urethane bond.
The polyethylene wax has a molecular mass of preferably 1,000 or less, more preferable from 300 to 1,000.
The compound having a urethane bond is preferred in that even if the compound has a low molecular mass, the compound can maintain a solid state by a strong cohesive force of a polar group and such a compound having a high melting point for the molecular mass thereof can be produced. The compound has a molecular mass of preferably from 300 to 1,000. Examples of a combination of materials for producing the compound include a combination of a diisocyanic acid compound and a monohydric alcohol, a combination of a monoisocyanic acid compound and a monohydric alcohol, a combination of a dihydric alcohol and a monoisocyanic acid compound, a combination of a trihydric alcohol and a monoisocyanic acid compound and a combination of a triisocyanic acid compound and a monohydric alcohol. However, for preventing the molecular mass of the compound from becoming too large, a combination of a compound having a multiple functional group and another compound having a single functional group is preferred and it is important that the total amount of the functionality in a combination is always equivalent.
Examples of the monoisocyanic acid compound include dodecyl isocyanate, phenyl isocyanate and derivatives thereof, naphthyl isocyanate, hexyl isocyanate, benzyl isocyanate, butyl isocyanate and allyl isocyanate, and the like.
Examples of the diisocyanic acid compound include tolylene diisocyanate, 4,4′ diphenylmethane diisocyanate, toluene diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate and isophorone diisocyanate, and the like.
Examples of the monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol and heptanol.
Examples of the dihydric alcohol include various glycols, such as ethylene glycol, diethylene glycol, triethylene glycol and trimethylene glycol. Examples of the trihydric alcohol include trimethylol propane, triethylol propane and trimethanol ethane.
These urethane compounds may be mixed with the resin or the colorant during kneading, as an ordinary releasing agent, and used also as a kneaded-crushed toner. Further, in a case of using an emulsion polymerization cohesion melting toner, the urethane compounds may be dispersed in water together with an ionic surfactant, polymer acid or polymer electrolyte such as a polymer base, heated above the melting point, and converted to fine particles by applying an intense shear in a homogenizer or pressure discharge dispersion machine to manufacture a releasing agent particle dispersion of 1 μm or less, which can be used together with a resin particle dispersion, colorant dispersion, or the like.
The amount of the releasing agent in the toner is not limited and may be properly selected depending on the application, and preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass.
Other Components for Toner—
The toner may comprise other components, such as an inner additive, a charge control agent and inorganic fine particles. Examples of the internal additives include magnetic substances such as ferrite, magnetite, reduced iron; and metals such as cobalt, nickel and manganese; the alloys thereof; and the compounds containing these metals.
Examples of the charge control agents include various charge control agents used usually, such as a quaternary ammonium salt, a nigrosine compound, a dye comprising a complex of a metal such as aluminum, iron and chromium and a triphenylmethane pigment. It is preferred that the charge control agents are difficultly dissolved in water, from the view point of controlling the ion strength which affect the stability during the cohesion and melting, and reducing the pollution by the waste water.
Examples of the inorganic particles include any of the external additives for toner surfaces generally used, such as silica, alumina, titania, calcium carbonate, magnesium carbonate and tricalcium phosphate. These particles are preferably used in the form of a dispersion produced by dispersing the particles in an ionic surfactant, a polymer acid or a polymer base.
Further, the toner may comprise as an additive surfactants for the emulsion polymerization, the seed polymerization, the pigment dispersion, the resin particles dispersion, the releasing agent dispersion, the cohesion and stabilization thereof. Examples of the surfactant include an anionic surfactant, such as a sulfate ester surfactants, sulfonate ester surfactants, phosphate ester surfactants and soaps; cationic surfactants, such as amine salt surfactants and a quaternary ammonium salt surfactants. It is also effective that the above-exemplified surfactants are used in combination with nonionic surfactants, such as polyethylene glycol surfactants, alkylphenol ethylene oxide adduct surfactants and polyhydric alcohol surfactants. As dispersing units for dispersing the surfactant in the toner, a general unit, such as a rotary shearing type homogenizer; and a ball mill, a sand mill and a dyno mill, all of which contain the media may be used.
The toner may comprise optionally outer additives. Examples of the outer additives include inorganic particles and organic particles. Examples of the inorganic particles include particles of SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO.SiO2, K2O.(TiO2)n, Al2O3.2SiOO2, CaCO3, MgCO3, BaSO4 and MgSO4. Examples of the organic particles include particles of a fatty acid and derivatives thereof; a metal salt of the above-noted fatty acid and derivatives thereof; and a resin, such as a fluorine resin, a polyethylene resin and an acrylic resin.
The average particle diameter of the above-noted particles is preferably from 0.01 μm to 5 μm, more preferably from 0.1 μm to 2 μm.
The manufacturing method of the toner is not limited and may be properly selected depending on the application. However, it is preferred that the toner is produced according to a manufacturing method of the toner comprising (i) preparing a dispersion of cohesive particles of resins by forming cohesive particles in a dispersion of particle resins, (ii) forming attached particles by mixing the above-prepared dispersion of cohesive particles with a dispersion of particles, so that the particles attaches to the cohesive particles, thereby forming attached particles and (iii) forming toner particles by heating the attached particles to be melted.
—Physical Properties of Toner—
The toner has a volume average particle diameter of preferably from 0.5 μm to 10 μm.
When the volume average particle diameter of the toner is too small, handling properties of the toner, such as replenish properties, cleaning properties and fluidity, may be affected adversely and the productivity of the particles may be lowered. On the other hand, when the volume average particle diameter of the toner is too large, the quality and resolution of the image due to graininess and transfer may be affected adversely.
It is preferred that the toner satisfies the above-noted range of a volume average particle diameter and has a distribution index of the volume average particle diameter (GSDv) of 1.3 or less.
The ratio (GSDv/GSDn) of the distribution index of the volume average particle diameter (GSDv) to the distribution index of the number average particle diameter (GSDn) is preferably 0.95 or more.
It is preferred that the toner satisfies the above-noted range of the volume average particle diameter and an average of the shape factor is preferably 1.00 to 1.50 which is calculated by the following equation:
Shape factor=(π×L2)/(4×S)
where “L” represents the maximum length of the toner particles and “S” represents the projected area of the toner particles.
When the toner satisfies the above-noted conditions, an effect on the image quality, such as graininess and resolution particularly can be obtained and moreover, dropout or blur which may accompany with the transfer is difficultly caused. Further, in this case, the handling properties of the toner may be difficultly affected adversely, even if the average particle diameter of the toner is not small.
From the viewpoint of improving the image quality and preventing the offset during the image-fixing, it is appropriate that the toner has storage elasticity modulus G′ (as measured at a circular frequency of 10 rad/sec) of 1×102 Pa to 1×105 Pa at 150° C.
The melting heat-transfer recording sheet, for example, comprises a support, and at least a heat-melting ink layer as an image-recording layer is disposed on the support, and is used in a method of transferring melted ink from heat-melting ink layer on a thermal transfer recording sheet by heating with a thermal head.
The sublimation-heat-transfer recording sheet comprises a support, and at least an ink layer comprising heat diffusive dye (subliming dye) is disposed on the support, and is used in a method of transferring sublimated heat diffusive dye from ink layer on a thermal transfer recording sheet by heating with a thermal head.
The heat-sensitive recording sheet comprises a support, and at least a heat-coloring layer is disposed on the support, and may be a heat-sensitive material used in a thermo-autochrome method (TA method) in which a repetition of heating by a thermal head and fixing by ultraviolet ray records an image.
The ink jet recording sheet, for example, comprises a support, and a porous-structured color-material-receiving layer is disposed on the support, in the color-material-receiving layer the following ink is absorbed in order to form an image. Examples of inks include liquid ink such as aqueous ink, which uses dye or pigment as a color material and oil ink, and solid ink a solid ink which is solid at room temperature and which is melted and liquefied when used for a print, and the like.
—Fusible Particle—
The fusible particle, substantially, is particle comprising transparent material, and as long as it can melt and form a continuous film during surface treating of the image recording material after image recording, is not limited and may be properly selected depending on the application, and comprises resin and preferably wax, and further, according to necessity, comprises other components.
The transparence means generally colorless transparence, and according to the kinds and amount of particle comprised therein, the transparency becomes lower a little, however, substantially, colorless transparence.
The resin, substantially, as long as it is transparent, may be properly selected depending on the application, for example, may be polyester resin, polystyrene resin, polyacryl resin, other vinyl resins, acrylic resin, polycarbonate resin, polyamide resin, polyimide resin, epoxy resin, polyurea resin, and ethylene/acryl copolymer, and the like. Among them, saturated polyester resin, saturated acrylic resin, saturated polystyrene resin, and crystalline polyolefin resin are preferable in particular.
The wax, as long as it has a melting point less than the heating temperature during the image recording, is not limited and may be properly selected depending on the application, for example, a synthetic hydrocarbon, modified wax, hydrogenated wax, natural wax, and the like and among them, natural wax is preferable.
Preferred examples of the natural wax include a vegetable wax, an animal wax, a mineral wax and a petroleum wax, and the like.
Examples of the vegetable wax include carnauba wax (EMUSTAR-0413, manufactured by Nippon Seiro Co., Ltd., serozoyl 524, manufactured by Chukyo Yushi Co., Ltd., as commercially available products), castor oil (refined castor oil manufactured by Itoh Oil Chemical Co., Ltd., as commercially available products), rape oil, soy bean oil, Japan tallow, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax and jojoba oil, and the like.
Examples of the animal wax include bees wax, lanolin, spermaceti wax, whale oil and wool wax, and the like.
Examples of the mineral wax include montan wax, montan ester wax, ozokerite, ceresin, and fatty acid esters (santicizer DOA, AN-800, DINA, DIDA, DOZ, DOS, TOTM, TITM, E-PS, NE-PS, E-PO, E-4030, E-6000, E-2000H, E-9000H, TCP, and C-1100, manufactured by New Japan Chemical Co., Ltd. as commercially available products), and the like.
Examples of the petroleum wax include paraffin wax (paraffin wax 155, 150, 140, 135, 130, 125, 120, 115, HNP-3, HNP-5, HNP-9, HNP-10, HNP-11, HNP-12, HNP-14G, SP-0160, SP-0145, SP-1040, SP-1035, SP-3040, SP-3035, NPS-8070, NPS-L-70, OX-2151, OX-2251, EMUSTAR-0384, EMUSTAR-0136, manufactured by Nippon Seiro Co., Ltd., serozoyl 686, 428, 651-A, A, H-803, B-460, E-172, 866, K-133, hydoline D-337, E-139, manufactured by Chukyo Yushi Co., Ltd., 125° paraffin, 125° FD, 130° paraffin, 135° paraffin, 135° H, 140° paraffin, 140° N, 145° paraffin, paraffin wax M, manufactured by Nisseki Mitsubishi Oil Co., Ltd., as commercially available products), microcrystalline wax (Hi-Mic-2095, Hi-Mic-3090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi-Mic-1045, Hi-Mic-2045, EMUSTAR-0001, EMUSTAR-042X, manufactured by Nippon Seiro Co., Ltd., serozoyl 967, M, manufactured by Chukyo Yushi Co., Ltd., 155 microwax, 180 microwax, manufactured by Nisseki Mitsubishi Oil Co., Ltd., as commercially available products), and petrolatum (OX-1749, OX-0450, OX-0650B, OX-0153, OX-261BN, OX-0851, OX-0550, OX-750B, JP-1500, JP-056R, JP-011P, manufactured by Nippon Seiro Co., Ltd., as commercially available products), and the like.
The amount of the wax in the fusible particle is preferably 0.1% by mass to 20% by mass. When the amount is less than 0.1% by mass, the releasing property deteriorates and adhesion resistance falls, and offset occurs easily in the heating and pressurizing treatment, and when it is more than 20% by mass, surface tackiness occurs on the surface.
Besides the above-mentioned thermoplastic resin, the fusible particle can comprise various components capable of mixing such as stabilizers, all types of fillers, and the like, at arbitrary ration.
The fusible particle may be commercially available or suitably synthesized ones. In the case of the latter, the synthesis method is not limited and may be properly selected depending on the application. Examples of the commercially available particles, may be Flo-Beads series manufactured by Sumitomo Seika Chemicals Co., Ltd., Flo-Thene series manufactured by Sumitomo Seika Chemicals Co., Ltd., Microgel series manufactured by Nippon Paint Co., Ltd. manufactured, and Mipelon series manufactured by Mitsui Chemicals, Inc, and the like.
The fusible particle, from the viewpoint of controlling fluidity and charging property, it is preferable to add or adhere on at least any one of outer additives of an inorganic particle and organic particle on the surface of the fusible particle.
The inorganic particle is not limited and may be properly selected from a group of well-known particles used as outer additives depending on the application. Examples of the material may be silica, titanium dioxide, stannic oxide, and molybdenum oxide, and the like. Also, considering the stability of charging property, those performing hydrophobing treatment by using silane coupling agent and titanium coupling agent against these inorganic particle, may also be used.
The organic particle is not limited and may be properly selected from a group of well-known particles used as outer additives depending on the application. Examples of the material may be polyester resin, polystyrene resin, polyacryl resin, other vinyl resins, polycarbonate resin, polyamide resin, polyimide resin, epoxy resin, polyurea resin, and fluorine resin, and the like.
The average particle diameter of these inorganic particle and organic particle is preferably 0.005 μm to 1 μm. When the average particle diameter is less than 0.005 μm, the desired effect may not be obtained because cohesion occurs when at least any one of the inorganic particle and organic particle is adhered on the surface of fusible particle. On the other hand, when it is more than 1 μm, it becomes difficult to obtain higher gloss image.
The fusible particle melts to form a continuous film during surface treatment of an image recording material after image recording, and the flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment after image recording. The flow starting temperature is preferably 70° C. or more, and more preferably 70° C. to 120° C.
When the flow starting temperature is less than 50° C., in the case of the environmental temperature becomes high, the sticking problem between sheets occurs easily, and when the flow starting temperature is more than the heating temperature in the surface treatment after image recording, fusible particle does not melt and a continuous film may not be obtained.
The volume average particle diameter of the fusible particle is 1 μm to 30 μm, and more preferably 1 μm to 20 μm, and still more preferably 2 μm to 15 μm. When the volume average particle diameter is less than 1 μm, the particle is transported difficultly, and when it is more than 30 μm, it becomes difficult to adhere particle uniformly on the image surface, and melt to form a uniformed continuous film.
—Hardly Fusible Particle—
The hardly fusible particle, as long as it is capable of maintaining a particle shape (including slightly transformed shape) without melting during surface treatment after image recording, is not limited and may be properly selected depending on the application, for example, at least any one of hardly fusible particle resin and inorganic particle is suitable.
The hardly fusible particle resin is preferably any one of transparent and colored. The colored one is preferablely white. For transparent, besides colorless transparent, colored transparent is also included.
The flow starting temperature of the hardly fusible particle resin is preferably higher than a heating temperature in the surface treatment after image recording. When the flow starting temperature of the hardly fusible particle resin is less than the heating temperature in the surface treatment, the hardly fusible particle resin is melted and transformed, and a change of the surface property may not be able to be obtained.
The hardly fusible particle resin, as long as the flow starting temperature is higher than the heating temperature in the surface treatment of an image recording material after image recording, is not limited and may be properly selected depending on the application, for example, may be polyester resin, polystyrene resin, polyacryl resin, other vinyl resins, polycarbonate resin, polyamide resin, polyimide resin, epoxy resin, urethane resin, melamine resin, fluorine resin, silicone resin, polyurea resin, and ethylene/acryl copolymer, and the like. Among them, urethane resin, epoxy resin, melamine resin, fluorine resin, and silicone resin are suitable.
For the hardly fusible particle resin, crosslinking particle is suitable. The crosslinking particle, for example, may be crosslinking acrylic resin, crosslinking styrene resin, crosslinking urethane resin, crosslinking polyester resin, crosslinking epoxy resin, crosslinking melamine resin, fluorine-containing setting-resin, and silicone-containing setting-resin, and the like.
The hardly fusible particle resin may be commercially available or suitably synthesized ones. In the case of the latter, the synthesis method is not limited and may be properly selected depending on the application. Examples of the commercially available particles may be Chemisnow series and Fine Powder series (both manufactured by Souken Chemicals Corporation), Techpolymer series and Micropearl series (both manufactured by Sekisui Chemical Co., Ltd.), Epostar series (manufactured by Nippon Shokubai Co., Ltd.) and Bellpearl (manufactured by Kanebo, Ltd.), and the like.
The inorganic particle is not limited and may be properly selected depending on the application, for example, silica, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, zinc oxide, zinc hydroxide, alumina, aluminium silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide, and yttrium oxide, and the like.
The hardly fusible particle, from the viewpoint of controlling fluidity and charging property, same as the fusible particle, it is preferable to add or adhere on at least any one of outer additives of inorganic particle and organic particle on the surface. For the outer additive, the same one as the above can be used.
The hardly fusible particle is preferably two kinds or more differing in at least any one of volume average particle diameter and shape from the viewpoint of capable of controlling surface property suitably.
The volume average particle diameter of the hardly fusible particle is 1 μm to 30 μm, and more preferably 2 μm to 30 μm, and still more preferably 3 μm to 20 μm. When the volume average particle diameter is less than 1 μm, the effect of surface unevenness becomes not able to be obtained, and when it is more than 30 μm, grittiness appears on the image, and clustering property declines.
The volume average particle diameter of the hardly fusible particle is preferably bigger than the thickness of the continuous film. In this case, since the hardly fusible particle projects from the outermost surface of the continuous film, the effect of surface unevenness can be obtained.
The particle size distribution of the hardly fusible particle is preferably 0.4 or less, and more preferably 0.35 or less. When the particle size distribution is less than 0.4, regular unevenness is formed on the image surface and steady high image quality is obtained.
When the particle size distribution is more than 0.4, in order to turn adhesion resistance and traveling performance to practical level, it is necessary to combine higher amount of fusible particle, and grittiness appears on the image quality.
Here, the particle size distribution, for example, can be measured by measuring arithmetic standard deviation and arithmetic mean diameter at a condition of performing ultrasonic dispersion for two minutes using particle size measuring apparatus (LA920, manufactured by Horiba, Ltd.), and the following equation; particle size distribution=(arithmetic standard deviation/arithmetic mean diameter).
The mixing ratio of the hardly fusible particle and the fusible particle (hardly fusible particle/fusible particle) is preferably 0.5/100 to 10/100, and more preferably 1/100 to 5/100. When the ratio of the hardly fusible particle is too much, it is difficult to form the continuous film, image quality deteriorates and it becomes fragile easily. On the other hand, when the ratio of the fusible particle is too much, the effect of surface unevenness may not be obtained.
The total adhesion amount of the fusible particle and the hardly fusible particle in the surface treating material in a first embodiment of the present invention is preferably 1 g/m2 to 30 g/m2, and more preferably 2 g/m2 to 20 g/m2. When the total adhesion amount is too little, it is difficult to form the continuous film, image quality deteriorates and it becomes fragile easily, and when it is too much, bended crack may occur.
The surface treating material in a second embodiment of the present invention comprises a base, and at least a surface layer comprising the fusible particle and the hardly fusible particle on the base, a releasing layer, and further comprises other layers if necessary.
The base, for example, maybe a plastic sheet, a metal sheet and a belt member, and the plastic sheet, for example, is preferable to comprise at least any one selected from polyimide, polyethylenenaphthalate, polyethylene terephthalate, polyetheretherketone, polyethersulfone, polyetherimide, and polyparabanic acid.
The base is preferably any one of a sheet shape, a belt shape and an endless belt shape, and among them, a belt shape is suitable.
The belt member comprises a support film and a releasing layer disposed on the support film.
The material for the support film, as long as it has heat resistance, is not limited and may be properly selected depending on the application. Examples of the material include polyimide (PI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyether ether ketone (PEEK), polyether sulfone (PES), poly ether imide (PEI) and poly parabanic acid (PPA), and the like. Among them, polyimide resin is suitable.
The releasing layer comprises preferably any one selected from the group consisting of a silicone rubber, a fluorine rubber, a fluorocarbon siloxane rubber, a silicone resin and a fluorine resin. Among them, the following aspects i) and ii): i) a fluorocarbon siloxane rubber layer disposed on the surface of the belt member and ii) a silicone rubber layer disposed on the surface of the belt member and a fluorocarbon siloxane rubber layer disposed on the surface of the silicone rubber layer are preferred.
The fluorocarbon siloxane rubber in the fluorocarbon siloxane rubber layer has preferably in the backbone chain thereof at least one of a perfluoroalkyl ether group and a perfluoroalkyl group.
The fluorocarbon siloxane rubber is preferably a cured product of a fluorocarbon siloxane rubber composition comprising the following components (A) to (D):
(A) a fluorocarbon polymer comprising mainly a fluorocarbon siloxane represented by the following formula (1) and having an unsaturated fatty hydrocarbon group, (B) at least one of organopolysiloxane and fluorocarbon siloxane which has two or more ≡SiH groups in a molecule, wherein the amount of a ≡SiH group is from one to four times (in mole) the amount of the unsaturated fatty hydrocarbon group in the above-mentioned fluorocarbon siloxane rubber composition, (C) a filler, and (D) an effective amount of catalyst.
The fluorocarbon polymer as the component (A) comprises mainly a fluorocarbon siloxane containing a repetition unit represented by the following formula (1) and contains an unsaturated fatty hydrocarbon group.
In formula (1), R10 represents an unsubstituted or substituted C1 to C8 monovalent hydrocarbon group and is preferably a C1 to C8 alkyl group or a C2 to C3 alkenyl group, most preferably a methyl group. “a” and “e” are respectively an integer of 0 or 1, “b” and “d” are respectively an integer of 1 to 4 and “c” is an integer of 0 to 8. “x” is preferably an integer of 1 or more, more preferably an integer of 10 to 30.
Examples of the component (A) include a compound represented by the following formula (2):
With respect to the component (B), examples of the organopolysiloxane having ≡SiH groups include an organohydrogen polysiloxane having in the molecule at least two hydrogen atoms bonded to a silicon atom.
In the fluorocarbon siloxane rubber composition, when the fluorocarbon polymer as the component (A) has an unsaturated fatty hydrocarbon group, as a curing agent, the above-mentioned organohydrogen polysiloxane is preferably used. In other words, the cured product is formed by an addition reaction between the unsaturated fatty hydrocarbon group of the fluorocarbon siloxane and a hydrogen atom bonded to a silicon atom in the organohydrogen polysiloxane.
Examples of the organohydrogen polysiloxane include various organohydrogen polysiloxanes used for curing a silicone rubber composition which is cured by an addition reaction.
The amount of the organohydrogen polysiloxane is an amount by which the number of ≡SiH group in the organohydrogen polysiloxane is preferably at least one, most preferably from 1 to 5, relative to one unsaturated fatty hydrocarbon group in the fluorocarbon siloxane of the component (A).
As for the fluorocarbon containing ≡SiH groups, R10 in the formula (1), as one unit or entire of the compound, is a dialkylhydrogen siloxy group, the terminal group is a ≡SiH group, such as a dialkylhydrogen siloxy group or a silyl group. Such a preferred fluorocarbon siloxane can be represented by the following formula (3).
As the filler which is the component (C), various fillers used for a usual silicone rubber composition can be used. Examples of the filler include areinforcing filler, such as mist silica, precipitated silica, carbon powder, titanium dioxide, aluminum oxide, quartz powder, talc, sericite and bentonite; and fiber filler, such as asbesto, glass fiber, and organic fiber, and the like.
As for the catalyst of component (D), the catalysts known in the art as addition reaction catalyst may be exemplified, such as chloroplatinic acid; alcohol-modified chloroplatinic acid; a complex of chloroplatinic acid with olefin; platinum black and palladium which are respectively supported on a carrier, such as alumina, silica and carbon; and Group VIII elements of the Periodic Table or compounds thereof such as a complex of rhodium with olefin, chlorotris(triphenylphosphine) rhodium (Wilkinson catalyst) and rhodium (III) acetyl acetonate. It is preferred that these complexes are dissolved in a solvent, such as an alcohol compound, an ether compound or a hydrocarbon compound to be used.
The fluorocarbon siloxane rubber composition is not limited and may be properly selected depending on the application, and optionally may comprise various additives. Examples of the various additives include a dispersing agent, such as diphenylsilane diol, low polymer of dimethyl polysiloxane in which the terminal of the molecule chain is blocked with a hydroxyl group, and hexamethyl disilazane; a heat resistance improver, such as ferrous oxide, ferric oxide, cerium oxide and iron octylate; and a colorant, such as a pigment, and the like.
The belt member can be obtained by coating a support film with the fluorocarbon siloxane rubber composition and by curing the resultant coated support film by the heating. Further optionally, for example, the belt member can be obtained by coating the support film with coating liquid prepared by diluting the fluorocarbon siloxane rubber composition with a solvent, such as m-xylene hexafluoride and benzotrifluoride, according to a general coating method, such as spray coating, dip coating and knife coating. The heat-curing temperature and time may be properly selected from the ranges of from 100° C. to 500° C. and from 5 seconds to 5 hours depending on the type of the support film and the manufacturing method of the belt.
—Surface Layer—
The surface layer comprises fusible particle and the hardly fusible particle, and further comprises other components, if necessary.
The total amount of the fusible fine particle and the hardly fusible fine particle is preferably 1 g/m2 to 30 g/m2, and more preferably 2 g/m2 to 20 g/m2. When the total amount is too little, it is difficult to form the continuous film, image quality deteriorates and it becomes fragile easily, and when it is too much, bended crack occurs.
The adhesion method of the fusible particle and the hardly fusible particle to the base is not limited and may be properly selected depending on the application, and may be an electrostatic adhesion, a coating, an impregnation, a spraying, and a dipping.
(Surface Treating Method)
The surface treating method of the present invention, in a first embodiment, comprises the adhering and the forming a surface treating layer, and further comprises others, if necessary.
The adhering is to adhere the surface treating material of the first embodiment of the present invention on the surface of the image recording layer of the image recording material after image recording.
The adhering can controlled any one of the adhesion amount of the surface treating material depending on the image information and the mixing ratio of hardly fusible particle and fusible particle.
The image information, for example, may be at least one selected from an image brightness, an image density, an image tone, an image size, and a combination thereof.
The adhering is not limited and may be properly selected depending on the application, and may be an electrostatic adhesion, a coating, an impregnation, a spraying, and a dipping.
The electrostatic adhesion is a method charging fusible particle and hardly fusible particle by the direct current high voltage obtained by a high voltage electrostatic generator, and adhering on the grounded image recording layer surface of the image recording material after image recording by electrostatic attraction, and it has an electrostatic spraying method and an electrostatic dipping method.
For the electrostatic spraying method, fusible particle and hardly fusible particle are sent from a supply vessel to a spray gun by air. According to high voltage (generally −40 kV to −90 kV) obtained by a high voltage electrostatic generator, fusible particle and hardly fusible particle obtain minus charge. On the other hand, the surface of the image recording layer of the image recording material after image recording is grounded, and fusible particle and hardly fusible particle emitted by the head of the gun are adhered on the surface of the image recording layer by an electrostatic attraction. At this time, minus-charged fusible particle and hardly fusible particle act strongly on the high potential part, and as fusible particle and hardly fusible particle adhered on the surface of the image recording layer adheres thickly, minus charge accumulated on the adhesion layer and when the thickness becomes more than a certain thickness, electrostatic repulsion is produced and adhesion becomes difficult.
For the electrostatic dipping method, the bottom plate of the dipping vessel loading the fusible particle and hardly fusible particle is comprised of a perforated plate, and the electrode is arranged at a fixed interval. The fusible particle and hardly fusible particle inside the vessel become a flowing state by the air stirred up from the porous bottom plate. On the other hand, high voltage of −40 kV to −90 kV is applied to the electrode by a high voltage electrostatic generator, and fusible particle and hardly fusible particle floating in the ionized air are minus-charged and lift up and whirl in the upper part inside the vessel, and are adhered on the surface of the grounded image recording layer of the image recording material after image recording. Particles which are not adhered on the surface of the image recording layer drop by gravity and again become charged particle and rise, and repeat the movement to adhere again on the surface of the image recording layer, and the adhesion of the particle is performed.
The coating is not limited and may be properly selected from a group of widely known coating methods depending on the application, for example, may be spin coating method, dip coating method, kneader coating method, curtain coating method, and blade coating method. Among them, spin coating method and dip coating method are preferable because of coating efficiency.
The surface treating layer forming forms a surface treating layer where hardly fusible particle is dispersed all over a continuous film formed by melting fusible particle by heating and pressurizing treatment.
The heating and pressurizing treatment is preferable to be performed using a belt surface treating device comprising a heating and pressurizing member, a belt member, and a cooler.
The heating and pressurizing member is not limited and may be properly selected depending on the application, for example, can be a pair of heating roller, and a combination of heating roller and pressurizing roller.
The cooler is not limited and may be suitably selected according to the purpose, for example, a cooler capable of blowing cold air and capable of controlling the cooling temperature and a heat sink, are used.
When contacting the heating and pressurizing member of the belt surface treating device, pressurizing is preferable. The pressurizing method is not limited and may be properly selected depending on the application, however, it is preferable to use nip pressure. The nip pressure is preferably 1 kgf/cm2 to 100 kgf/cm2 and more preferably 5 kgf/cm2 to 30 kgf/cm2. The heating temperature at the heating and pressurizing member is preferably 80° C. or more and more preferably 100° C. to 180° C. The cooling temperature in the cooler is preferably 80° C. or less and more preferably 20° C. to 80° C.
For the belt member, the above-mentioned belt member can be used similarly.
Here, as a surface treating apparatus for carrying out surface treating process involving in the first embodiment, the apparatus shown in
In
Also, in the inner surface of the above-mentioned endless belt 6, between assistance rollers 8, 9, cooler 10 are provided.
In the above-mentioned heat transferring region 12, the image medium 2 inserted from the insert opening 3 is contacted with the endless belt 6 where the fusible particle and hardly fusible particle are adhered by the assistance roller 8 and heating roller 14 having built-in halogen heating lamp 13 for melting the fusible particle. And, this image medium 2 is cooled by cooler 10 through endless belt 6, and after conveyed to assistance roller 9 at which only the image medium disposing with the surface treating layer is removed by blade 15, then, the image medium can be taken out from the take-out opening 4.
This embodiment comprises transfer fixing mechanism K1 is constructed from assistance roller 8, halogen heating lamp 13, and heating roller 14.
In the above-mentioned adhesion region 11, rotatable support roller 16 is arranged so as to contact the conveyance route of endless belt 6 with a certain space at its circumference surface. Transfer electric field is acted between support roller 16 and conveyance roller 7 by power source E. Rotatable feeding roller 17 is contacted with support roller 16 by pressing at the upper point of the rotating direction of support roller 16 compared to adhesion region 11. Feeding roller 17 is covered by particle case 18, and in particle case 18, fusible particle and hardly fusible particle are stored. This embodiment comprises charge coating mechanism K2 is constructed from sheet conveyance roller 7, support roller 16, feeding roller 17 and power source E.
By the rotation of support roller 16 and feeding roller 17, fusible particle and hardly fusible particle are contacted and charged by friction, and the uniformly charged fusible particle and hardly fusible particle adheres on support roller 16, and then the fusible particle and hardly fusible particle adhered on support roller 16 are electrostatically stuck to endless belt 6 by transfer electric field by power source E.
Here, the operation of the surface treating apparatus is described.
Firstly, by the rotation of support roller 16 and feeding roller 17, fusible particle and hardly fusible particle contacted and charged by friction, and then the uniformly charged fusible particle and hardly fusible particle are adhered on support roller 16.
On the other hand, endless belt 6 is conveyed by the rotation of rotation roller 5, and in coating region 11, according to applying minus voltage of the polarity opposite to the polarity of the plus-charged fusible particle and hardly fusible particle to sheet conveyance roller 7 by power source E, thereby fusible particle and hardly fusible particle are electrostatically stuck to adhere from support roller 16 onto endless belt 6. At this time, endless belt 6 itself comprises insulation property and the injection of charge to non-coated region is not occurred during the above-mentioned electrostatic adsorption, therefore, fusible particle and hardly fusible particle can be coated effectively and uniformly with endless belt 6.
Next, image medium 2 which image is output inserted from the insert opening 3 and the endless belt 6 with which fusible particle and hardly fusible particle are coated, contacted by pressing with assistance roller 8 and heating roller 14. At this time, according to the heat generated by halogen heating lamp 13 built in heating roller 14, fusible particle is melted, and further, a transparent surface treating layer is formed between image medium 2 and endless belt 6 by the compressive force of assistance roller 8 and heating roller 14. And, these are conveyed by rotation of assistance roller 8, 9, and in the meantime, cooled by cooler 10 through endless belt 6, and the transparent surface treating layer is cured.
Finally, as the endless belt excels in separating property, the image medium is separated by blade 15 while the transparent surface treating layer is completely left on the image medium, and the image medium 2 where the surface treating layer is formed can be taken out from take-out opening 4.
In a second embodiment, the surface treating process of the present invention, comprises lamination layer forming and surface treating layer forming, and further, according to necessity, comprises others.
The lamination layer forming is to form a lamination layer by putting together with heating and pressurizing treatment a surface layer of a surface treating material of the second embodiment of the present invention on the surface of an image recording layer of an image recording material after image recording.
The surface treating layer forming forms a surface treating layer where hardly fusible particle is dispersed in a continuous film in which fusible particle is melted by heating and pressurizing treatment.
The heating and pressurizing treatment is preferably performed using a belt surface treating device comprising heating and pressurizing member, and belt member. The heating and pressurizing member and belt member are the same as the surface treating process in the above-mentioned first embodiment.
As a surface treating apparatus for carrying out surface treating process in the second embodiment, the apparatus shown in
The surface treating region of manuscript 23 put on manuscript platform 24 is specified, and when the information is input into CPU (not shown), CPU calculates writing timing and the others of the specific region, and necessary information is sent to LED array 33 arranged in a line facing surface treating layer forming body 1A and in a axis direction of surface treating layer forming body 1A. By charger 19, on uniformly charged surface treating layer forming body 1A, in which the surface layer comprises inorganic photoconductivity material and organic photoconductivity material such as selenium, silicon and cadmium sulfide, light exposure and electric elimination of a pattern part corresponding to the specific surface treating region of manuscript 23 is exposed and electricity is removed by LED 33, and then an electrostatic latent image is formed.
The Specified fusible particle and hardly fusible particle from particle supply device 40 are supplied to the electrostatic latent image adhered on surface treating layer forming body 1A. Fusible particle and hardly fusible particle are charged to the same polarity as the uniform charge on surface treating layer forming body 1A by friction. At the time of this non-contact phenomenon, from the power source (not shown), a phenomenon bias where alternating current component of bias potential 1.8 kV and frequency 8 kHz overlapped on direct current component of bias potential −750V is applied to sleeve 34. A result, an action of selectively conveying fusible particle and hardly fusible particle on sleeve 34 of phenomenon contacting part to the latent image on the surface treating layer forming body 1A is accomplished. According to this, fusible particle and hardly fusible particle are moved and absorbed to surface treating layer forming body 1A one by one by an electrostatic force of the electrostatic latent image, and fusible particle and hardly fusible particle are adhered at a specific pattern. Bias is controlled and applied to the sleeve, and the adhesion amount can be controlled.
The adhered fusible particle and hardly fusible particle, if necessary, is recharged in order to improve transfer rate, and then, is transferred by transferring device 30 onto image recording medium 7A after image recording, which is conveyed from image recording medium conveying device 28 through paper feeding roller 22 so as to correspond with the image region on surface treating layer forming body 1A by timing roller 23. Image recording medium 7A where particle image on surface treating layer forming body 1A is transferred, is separated from surface treating layer forming body 1A by separating pole 26 and sent to belt fixing device 6A. On the other hand, surface treating layer forming body 1A transferring particle image to image recording medium 7A, subsequently continues to rotate in the direction of the arrow, and after charge removed by charge removing device 31, particles adhered on surface treating layer forming body 1A is removed by cleaning blade 29A provided in cleaning device 29. And, again, surface treating layer forming body 1A is charged by charger 19 and proceeds to the next transferring.
According to the driving rotation heating roller 42, the endless belt 41 is revolved and conveyed a clockwise direction. 45 denotes a pressurizing roller contacting the circumference surface of the endless belt 41 winding heating roller 42, is driven in an anticlockwise direction or driven rotatably at the same speed as heating roller 42, and image recording medium 7A on which particle image is transferred, is attached between pressurizing roller 45 and endless belt 41 and conveyed. The pressurizing roller 45 provides high hardness with heating roller 42, and endless belt 41 is pressed to heating roller 42 so as to form a first nip region.
The heating roller 42 and pressurizing roller 45 comprise the same outside dimension and each has a built-in heater H1 and H2 with the same heat value respectively, and the temperature of the circumference surface is controlled and managed by temperature detection of each temperature sensor S1 and S2 respectively. F1 and F2 are crossflow fan (hereinafter referred to as merely “fan” below), which is a cooling unit provided at in and out side of conveyance surface of endless belt, the air inhaled from the outside of the apparatus through duct 47A and 47B respectively, fan F1 blows the inhaled air which passes through several slit holes 46A opening in conveyance guide plate 46 directly cools the lower surface of image recording medium 7A on which the particle image is transferred, on the other hand, fan F2 blows the inhaled air at the inner surface of endless belt 41 which indirectly cools the upper surface of image recording medium 7A. Further, for each cleaning roller 41A and 45A that clean particle adhered on each circumference surface of endless belt 41 winding heating roller 42 and pressurizing roller 45, and further, in order to prevent the adhesion of particle oil impregnated roller 41B is contacted by pressing on endless belt 41.
The fixing action of particle image on image recording medium 7A by the fixing device is described.
When image recording medium 7A where particle image is adhered on the upper surface, is conveyed into the inside of the apparatus as the arrow A direction in
And then, after passing through the nip region, the melted particle is adhered firmly to image recording medium 7A.
For the surface treating process of the present invention, the change of the surface property is preferably at least one part of the surface of the image recording layer, and can be the entire surface of the image recording layer.
The surface property may be selected from any one of a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
The surface property is preferably changeable depending on the selection by a user.
For the present invention, the surface property is changed by changing any one of a total adhesion amount of the surface treating material corresponding to image information, a combination of the hardly fusible particle and fusible particle, and a mixing ratio of the hardly fusible particle and fusible particle.
The image information may be preferably at least one selected from an image brightness, an image density, an image tone, an image size and a combination thereof. For example, gloss can be given to a background part of a sheet body. As high brightness part becomes bright and dark part becomes matte by distributing the gloss a three-dimensional effect can be given to the image.
According to the surface treating process of the present invention, the surface treating layer comprises a sea-island structure where fusible particle melts during surface treatment after image recording and hardly fusible particle is disperses all over a formed continuous film.
Surface property of at least one part of the surface of the image recording of the image recording material is capable of changing.
The volume average particle diameter of the hardly fusible particle is preferably bigger than the thickness of the surface treating layer. According to this, since the hardly fusible particle projects from the outermost surface of the surface treating layer, the effect of surface unevenness can be obtained.
The image recording material can be used in at least any one selected from image-receiving sheet for electrophotography, melting heat transfer recording sheet, sublimation heat transfer recording sheet, thermographic recording sheet, and ink jet recording sheet.
The present invention will be illustrated in further details with reference to the examples below, which are never intended to limit the scope of the present invention.
EXAMPLES 1 TO 8 AND COMPARATIVE EXAMPLES 1 TO 4—Image Forming—
A full-color image was formed by a Fuji Film Xerographic Paper A4 size for Photo Recipe (manufactured by Fuji Photo Film Co., Ltd.) as an image forming paper, and an image forming apparatus DC 1250PF (manufactured by Fuji Xerox Co., Ltd.).
—Preparation of Particle—
Hardly fusible particle shown in the Table 2 and fusible particle shown in the Table 3 were used. For the particle, SiO4 particle (the surface was hydrophobic treated by silane coupling agent, average particle diameter of 0.05 μm) was adhered on the surface as an object to control fluidity and charging property. The adhesion amount of SiO4 particle is 1 part by mass based on particle 100 part by mass.
—Hardly Fusible Particle—
Chernisnow MX2000, manufactured by Souken Chemicals Corporation Techpolymer XX08S, Techpolymer SBX-12, manufactured by Sekisui Plastics Co., Ltd.
Tospearl 145, manufactured by GE Toshiba Silicones Company Limited.
Tipaque TTO-51, manufactured by Ishihara Industry Sangyo Kaisha Ltd.
Aerosol OX-50, manufactured by Japan Aerosol Co., Ltd.
The particle size distribution in Table 1 was measured that arithmetic standard deviation and arithmetic mean diameter was measured at a condition of ultrasonic dispersion for two minutes by particle size measuring apparatus (LA920, manufactured by Horiba, Ltd.), and the following equation, particle size distribution = (arithmetic standard deviation/arithmetic mean diameter).
—Fusible Particle—
Flo-Beads LE1080, CL2080 and EA209, all manufactured by Sumitomo Seika Chemicals Co., Ltd.
Prototype a was classified by wind force type classifier after crushing polymer (polyester resin) obtained by reacting terephthalic acid 100 mol as acid component, and alcohol component 100 mol comprising bisphenol A-ethylene glycol adduct 20 mol % and ethylene glycol 80 mol % by jet mill.
Prototype b was classified by wind force type classifier after crushing polymer (polyester resin) obtained by reacting acid component 100 mol comprising terephthalic acid 80 mol % and sebacic acid 20 mol %, and alcohol component 100 mol comprising bisphenol A-ethylene glycol adduct 90 mol % and ethylene glycol 10 mol % by jet mill.
Prototype c was classified by wind force type classifier after crushing polymer (polyester resin) obtained by reacting acid component 100 mol comprising terephthalic acid 40 mol % and sebacic acid 60 mol %, and alcohol component 100 mol comprising bisphenol A-ethylene glycol addition product 90 mol % and ethylene glycol 10 mol % by jet mill.
In Table 3, flow starting temperature was measured base on JIS K 7210.
<Forming Method of Surface Treating Layer (I)>
Using the surface treating apparatus shown in
—Transfer Electric Field—
3 kV
—Belt—
Support of the belt: polyimide (PI) film, width of 50 cm, thickness of 80 μm
Releasing layer material of the belt : SIFEL 610, a fluorocarbon siloxane rubber precursor (manufactured by Shin-Etsu Chemical Co., Ltd.) was vulcanized to form a fluorocarbon siloxane rubber of 50 μm thick.
—Heating and Pressurizing—
Temperature of heating roller: 130° C.
Nip pressure: 130N/cm2
—Cooling—
Cooler :heat sink length of 80 mm
Conveyance Speed: 53 mm/sec
Temperature: 80° C.
Next, for each obtained image print after surface treatment, traveling performance, image quality (gloss), appearance (silk-finish photoprint style), granularity, adhesion resistance, and fingerprint adhesive property were evaluated according to the following conditions. The results are shown in Table 5.
<Evaluation of Appearance (Silk-Finish Photoprint Style)>
For the obtained full-color image, under an interior illumination, sensory evaluation was performed based on the following standard.
[Evaluation Standard]
A . . . high quality and stable silk-finish photoprint style
B. . . quality to a certain degree
C . . . not sufficient
D . . . grittiness and glitter
<Evaluation of Image Quality (Gloss)>
Density was painted to 6 levels (0, 20, 40, 60, 80, 100%) in every 10 square-centimeter size under B/W condition during image forming. This 6 leveled parts, based on JIS Z 8741 was measured at 20° measurement by a digital deflection glossmeter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.), and the minimum value was recorded. For the present invention, 20° gloss is preferably 75 or more.
<Evaluation of Adhesion Resistance>
For the obtained image print, after the adjustment for 24 hours at 40° C. under 80% Relative Humidity, putting together with facing toner image surface, 500 g was loaded in 3.5 square-centimeter, and after being left for 7 days under the same environment, a state where the sample was peeled off was evaluated according to the following standard. In the present invention, the adhesion resistance is preferably 2 or less.
[Evaluation Standard]
1 . . . no peeling sound and no adhesion trace
2 . . . a light peeling sound or an adhesion trace
3 . . . adhesion trace is less than 25%
4 . . . less than 25% to 50% is adhered
5 . . . more than 50% is adhered
<Evaluation of Fingerprint Adhesive Property>
After pressing thumb on the image surface of the image print after image recording, under an interior illumination, fingerprint adhesive property was evaluated according to the following standard. The evaluation results were shown by the average of 10 panelists.
[Evaluation Standard]
A . . . adhesion of fingerprint is extremely weak
B . . . adhesion of fingerprint is weak
C . . . fingerprint trace can be seen a little strongly
D . . . fingerprint trace can be seen strongly and clearly
<Evaluation of Traveling Performance (Clustering)>
Image print was discharged from the surface treating layer forming apparatus and when it was accumulated in an accumulation case, the number that became irregular is shown.
<Evaluation of Granularity>
The evaluation of granularity was performed by visual evaluation using uniformed images of 2 square-centimeter size differing in average reflection density. The evaluation was performed by assessors of 20 people according to the following 5 levels.
[Evaluation Standard]
1 . . . texture is extremely rough
2 . . . texture is rough
3 . . . normal
4 . . . texture is fine
5 . . . texture is extremely fine.
Next, the result of the average value was found and evaluated by the following standard.
A . . . when the average is more than 4
B . . . when the average is more than 2 and less than 4
C . . . when the average is less than 2
—Image Forming—
A full-color image was formed by an ink jet recording paper (Kassai WPA420A, manufactured by Fuji Photo Film Co., Ltd.) as the image recording paper, and an ink jet printer (manufactured by Seiko-Epson Corporation, PM-800C).
—Preparation of Particle—
Particle mixture was prepared by using the particle in Table 2 and Table 3 with the combination shown in Table 6.
<Forming Method of Surface Treating Layer (II)>
Using the surface treating apparatus shown in
—Transfer Electric Field—
3 kV
—Belt—
Support of the belt: polyimide (PI) film, width of 50 cm, thickness of 80 μm
Releasing layer material of the belt: SIFEL 610, a fluorocarbon siloxane rubber precursor (manufactured by Shin-Etsu Chemical Co., Ltd.) was vulcanized to form a fluorocarbon siloxane rubber of 50 μm thick.
—Heating and Pressurizing—
Temperature of heating roller: 130° C.
Nip pressure: 130N/cm2
Next, for each obtained image print after surface treatment, same as the Examples 1 to 8 and Comparative Examples 1 to 4, traveling performance, image quality (gloss), appearance (silk-finish photoprint style), granularity, adhesion resistance, and fingerprint adhesive property were evaluated. The results are shown in Table 7.
The surface treating material and a surface treating method of the present invention are capable of giving effectively surface property selected from any one of a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof on the surface of the image recording layer of an image recording material after image recording, for example, can be used widely in an image-receiving sheet for electrophotography, a melting heat-transfer-recording sheet, a sublimation heat-transfer-recording sheet, a thermographic recording sheet, and an ink jet recording sheet.
Claims
1. A surface treating material comprising:
- a fusible particle and a hardly fusible particle which are used for changing a surface property on a surface of an image recording layer of an image recording material after image recording, wherein the fusible particle is melted to form a continuous film by a surface treatment, and a flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment, and
- wherein the hardly fusible particle is not melted with maintaining a particle shape by the surface treatment, and a volume average particle diameter of the hardly fusible particle is 1 μm to 30 μm.
2. The surface treating material according to claim 1, wherein the surface treating material comprises a base, and a surface layer comprising the fusible particle and the hardly fusible particle disposed on or above the base.
3. The surface treating material according to claim 2, wherein the surface treating material comprises a releasing layer comprising a releasing agent between the base and the surface layer.
4. The surface treating material according to claim 2, wherein the base is any one of a sheet shape, a belt shape, and an endless belt shape.
5. The surface treating material according to claim 1, wherein a total adhesion amount of the fusible particle and the hardly fusible particle in the surface layer is 1 g/m2 to 30 g/m2.
6. The surface treating material according to claim 1, wherein the surface property is changed on at least a part of the surface of the image recording material.
7. The surface treating material according to claim 1, wherein the surface property is any one selected from a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
8. The surface treating material according to claim 1, wherein the surface treating material comprises a sea-island structure in a state where the hardly fusible particle is dispersed with maintaining the particle shape in the continuous film.
9. The surface treating material according to claim 1, wherein a mixing mass ratio of the hardly fusible particle and the fusible particle (hardly fusible particle/fusible particle) is 0.5/100 to 10/100.
10. The surface treating material according to claim 1, wherein the fusible particle is transparent and a volume average particle diameter is 1 μm to 30 μm.
11. The surface treating material according to claim 1, wherein a volume average particle diameter of the hardly fusible particle is 2 μm to 30 μm and bigger than a thickness of the continuous film.
12. The surface treating material according to claim 1, wherein a particle size distribution of the hardly fusible particle is 0.4 or less.
13. The surface treating material according to claim 1, wherein the hardly fusible particle is of 2 kinds or more differing in at least any one of volume average particle diameter and shape.
14. The surface treating material according to claim 1, wherein the hardly fusible particle comprises any one of the hardly fusible particle resin and an inorganic particle.
15. The surface treating material according to claim 14, wherein a flow starting temperature of the hardly fusible particle resin is higher than the heating temperature in the surface treatment.
16. The surface treating material according to claim 14, wherein the hardly fusible particle resin is a crosslinking particle, and the crosslinking particle comprises any one selected from a crosslinking acrylic resin, a crosslinking styrene resin, a crosslinking urethane resin, a crosslinking polyester resin, a crosslinking epoxy resin, a crosslinking melamine resin, a fluorine-containing setting-resin and a silicone-containing setting-resin.
17. The surface treating material according to claim 1, wherein the fusible particle comprises any one selected from a saturated polyester resin, an acrylic resin, a polystyrene resin and crystalline polyolefin resin.
18. The surface treating material according to claim 1, wherein the fusible particle comprises a wax, and a melting point of the wax is less than the heating temperature in the surface treatment.
19. The surface treating material according to claim 1, wherein the image recording material is any one selected from an image-receiving sheet for electrophotography, a recording sheet of melting and heat transfer, a recording sheet of sublimation and heat transfer, a thermosensitve recording sheet and an ink jet recording sheet.
20. A surface treating process comprising:
- adhering a surface treating material on a surface of an image recording layer of an image recording material after image recording,
- forming a surface treating layer on the surface of the image recording layer of the image recording material after image recording, and
- wherein the surface treating material comprises a fusible particle and hardly fusible particle for changing a surface property of the image recording layer of the image recording material after image recording and,
- wherein the fusible particle is melted to form a continuous film by a surface treatment, and a flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment, and wherein the hardly fusible particle is not melted with maintaining a particle shape by the surface treatment, and a volume average particle diameter of the hardly fusible particle is 1 μm to 30 μm, and wherein the hardly fusible particle is dispersed in a continuous film which is formed by melting the fusible particle by a heating and pressurizing treatment.
21. The surface treating process according to claim 20, wherein a adhesion is performed by any one of an electrostatic adhesion, a coating, an impregnation, a dipping and a spraying.
22. The surface treating process according to claim 20, wherein the heating and pressurizing treatment is performed using a belt surface treating device comprising a heating and pressurizing member, a belt member and a cooler.
23. The surface treating process according to claim 20, wherein a total adhesion amount of the fusible particle and the hardly fusible particle is 1 g/m2 to 30 g/m2.
24. The surface treating process according to claim 20, wherein the surface treating material is adhered on at least a part of an image recording surface of the image recording material.
25. The surface treating process according to claim 20, wherein the surface property is changed by changing any one of a total adhesion amount of the surface treating material depending on an image information, a combination of the hardly fusible particle and the fusible particle, and a mixing ratio of the hardly fusible particle and the fusible particle.
26. The surface treating process according to claim 25, wherein the image information is at least any one selected from an image brightness, an image density, an image tone, an image size, and a combination thereof.
27. The surface treating process according to claim 20, wherein a heating temperature in the heating and pressurizing treatment is 80° C. or more.
28. The surface treating process according to claim 20, wherein the surface property can be changed depending on a selection by a user.
29. The surface treating process according to claim 28, wherein the surface property is any one selected from a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
30. A surface treating process comprising:
- forming a laminated body by putting together a surface layer of a surface treating material and an image recording layer of the image recording material after image recording by heating and pressurizing treatment,
- forming a surface treating layer by cooling and separating the laminated body from a base, and
- wherein the surface layer of the surface treating material comprising a fusible particle and hardly fusible particle are deposed on a base, wherein the surface layer changes a surface property of the image recording layer of the image recording material after image recording, wherein the fusible particle is melted to form a continuous film by a surface treatment, and a flow starting temperature of the fusible particle is 50° C. or more, and less than a heating temperature in the surface treatment, and wherein the hardly fusible particle is not melted with maintaining a particle shape by the surface treatment, and a volume average particle diameter is 1 μm to 30 μm, and
- wherein the a surface treating layer comprises the hardly fusible particle is dispersed in the continuous film which is formed by melting the fusible particle.
31. The surface treating process according to claim 30, wherein the heating and pressurizing treatment is performed using a belt surface treating device comprising a heating and pressurizing member, a belt member and a cooler.
32. The surface treating process according to claim 30, wherein a heating temperature in the heating and pressurizing treatment is 80° C. or more.
33. The surface treating process according to claim 30, wherein the surface property can be changed depending on a selection by a user.
34. The surface treating process according to claim 30, wherein the surface property is any one selected from a matte, a semimatte, an emboss, a luster, a silk finish, and a combination thereof.
Type: Application
Filed: Aug 24, 2005
Publication Date: Mar 2, 2006
Applicant: FUJI PHOTO FILM CO., LTD. (Minami-Ashigara-shi)
Inventor: Yoshio Tani (Shizuoka)
Application Number: 11/209,668
International Classification: D04H 13/00 (20060101);
