Solid Polymer Utilized Contains Vinyl Alcohol Units Patents (Class 524/459)
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Patent number: 5705553Abstract: Copolymers containing carboxyl groups in aqueous dispersion form or redispersible powder form and their water-soluble salts, based on ethylenically unsaturated and copolymerizable monomers, the macro-molecules of which contain at least 24% by weight of monomer units carrying carboxyl groups prepared, by emulsion copolymerization initiated by free radicals in the presence of polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) dissolved in the aqueous phase and isolation of the copolymers in aqueous dispersion form, and optionally subsequent removal of water by spray drying to obtain redispersible copolymer powders and processes for their preparation and their use as thickeners in aqueous formulations which copolymers, by conversion into their water-soluble salt forms, are useful as thickening agents having a surprisingly advantageous rheology-modifying action in aqueous systems.Type: GrantFiled: November 13, 1995Date of Patent: January 6, 1998Assignee: Hoechst AktiengesellschaftInventor: Rolf Kuropka
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Patent number: 5686518Abstract: An essentially stable monomer miniemulsion characterized by small monomer droplet size is prepared and is then polymerized to a polymer latex under free radical polymerization conditions. The monomer miniemulsions herein include, in addition to water, a surfactant, and a monomer or mixture thereof, one or more polymers which function as a polymeric co-surfactant. The monomer miniemulsions are characterized by average monomer droplet size of 10 to 500 nanometers, preferably 80 to 150 nanometers. The amount of polymer added as a co-surfactant is about 0.5 to about 5 percent by weight based on monomer weight. The monomer emulsion may contain either a single monomer or a monomer mixture. The monomer emulsion is polymerized under conventional emulsion polymerization conditions yielding a polymer latex having an average polymer particle size of 10 to 500 nanometers, preferably 80 to 150 nanometers, and a narrow particle size distribution, i.e., a polydispersity index of about 1.05 to about 1.40.Type: GrantFiled: January 3, 1995Date of Patent: November 11, 1997Assignee: Georgia TechInventors: Kevin J. Fontenot, F. Joseph Schork, Jay L. Reimers
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Patent number: 5684079Abstract: A curing composition for reinforcing an inorganic oxide material or a flawable base is disclosed. The composition comprises a curing compound emulsified and dispersed in water with or without the aid of an emulsifier or a water-soluble high polymer. The composition has excellent preservation stability and is free from the risk of fire or environmental pollution. The process for reinforcing an inorganic oxide material or a flawable base using the composition is also disclosed.Type: GrantFiled: November 19, 1991Date of Patent: November 4, 1997Assignee: Dainippon Ink and Chemicals Inc.Inventors: Masanobu Yumoto, Tsutomu Imai, Hiromu Chano, Torao Higuchi, Yutaka Hashimoto, Masayuki Kamei
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Patent number: 5679735Abstract: A process for the preparation of a synthetic resin dispersion stabilized by a protective colloid employing at least one initiator and based on a polymer of (a) a first monomer of at least one ester of acrylic acid or methacrylic acid and an alcohol containing 1 to 22 carbon atoms; and optionally, (b) a second monomer which can be copolymerized with the first monomers. The process comprises introducing at least 50% of the monomers based on the total weight of the monomers, at least 50% of the protective colloid based on the total weight of the protective colloid, and up to 50% of the initiator based on the total weight of the initiator into a reaction vessel to form an aqueous emulsion. Any remaining monomers and protective colloid and at least 50% of the initiator based on the total weight of the initiator are then added to the reaction vessel at a temperature of 30.degree. to 100.degree. C.Type: GrantFiled: December 22, 1995Date of Patent: October 21, 1997Assignee: Hoechst AktiengesellschaftInventors: Ulrich Geissler, Helmut Rinno, Heinz-Josef Thevissen
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Patent number: 5677365Abstract: An aqueous resin dispersion for a heat-sensitive recording material is disclosed. The aqueous resin dispersion is obtained by the use of polyvinyl alcohol as an emulsifier and the use of two steps of polymerization. In the first step of polymerization, a polymeric monomer composition A is polymerized, composition A containing polymeric multi-functional monomers which constitute 15% by weight or more of the total weight of the polymeric monomers used for the first step. And, in the second step, a polymeric monomer composition B is polymerized, The invention also discloses a heat-sensitive recording material using such an aqueous resin dispersion as a color-developing layer or a protective coating.Type: GrantFiled: February 3, 1994Date of Patent: October 14, 1997Assignee: Nippon Shokubai Co., Ltd.Inventors: Teruo Kikuta, Katsuyuki Kono
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Patent number: 5652289Abstract: A method for making a polymer, includes the step of polymerizing a mixture of a vinyl ester monomer, a (C.sub.1 -C.sub.12)alkyl (meth)acrylate monomer and a mono ethylenically unsaturated polar monomer by free radical initiated polymerization in an aqueous medium and in free presence of a colloidal stabilizer, a first poly(alkoxylated) alkyl phenol having less than or equal to 12 alkoxyl units per molecule and a second poly(alkoxylated) alkyl phenol having greater than 12 alkoxyl units per molecule, to form an emulsion of the polymer in the aqueous medium.Type: GrantFiled: October 11, 1995Date of Patent: July 29, 1997Assignee: Rohm and Haas CompanyInventors: Eric Karl Eisenhart, Bradley Anson Jacobs
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Patent number: 5652293Abstract: A method for making a polymer includes adding a first portion of a colloidal stabilizer to an aqueous medium, adding a monomer mixture, said monomer mixture including a monomer charge and a second portion of colloidal stabilizer and said monomer charge including from about 40 parts by weight to about 70 parts by weight of a vinyl ester monomer per 100 parts by weight monomer charge and from about 30 parts by weight to about 60 parts by weight of a (C.sub.1 -C.sub.12)alkyl (meth)acrylate monomer per 100 parts by weight monomer charge, to the aqueous medium and polymerizing the monomers to form an emulsion of the polymer in the aqueous medium.Type: GrantFiled: October 25, 1995Date of Patent: July 29, 1997Assignee: Rohm and Haas CompanyInventors: Eric Karl Eisenhart, Bradley Anson Jacobs, Louis Christopher Graziano
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Patent number: 5635566Abstract: Process for preparing dispersions stabilized with protective colloid using sulfonato-containing polyvinyl acetals as the protective colloid in the preparation of the dispersions, if desired in combination with additional emulsifiers or additional protective colloids. The dispersions exhibit a pH-dependent viscosity and are suitable, for example, for coating and bonding substrates and as rheology modifiers and binders and for use in solid paints.Type: GrantFiled: November 28, 1994Date of Patent: June 3, 1997Assignee: Hoechst AktiengesellschaftInventors: Bettina Gerharz, Matthias Kroggel
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Patent number: 5629370Abstract: A vinyl acetate-ethylene copolymer emulsion having a solids content of at least 65 percent by weight is disclosed. Specifically, the copolymer emulsion comprises about 5 to 40 percent by weight ethylene, about 60 to 95 percent by weight vinyl acetate, about 0.8 to 2.0 percent by weight of a fully or partially hydrolyzed polyvinyl alcohol, and a mixture of nonionic ethoxylated alkyl phenol surfactants having a HLB of from about 16.0 to 16.5.Type: GrantFiled: April 29, 1996Date of Patent: May 13, 1997Assignee: Reichhold Chemicals, Inc.Inventor: Yakov S. Freidzon
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Patent number: 5599870Abstract: The present invention relates to an aqueous emulsion comprising a dispersant of a modified polyvinyl alcohol with an ethylene unit content of 2 to 9 mol % and a degree of hydrolysis of at least 95 mol %, a dispersoid of a polymer of an ethylenically unsaturated monomer, and a ratio (.eta.2 rpm/.eta.20 rpm) of Brookfield viscosity at 30.degree. C., 2 rpm (.eta.2 rpm) as against Brookfield viscosity at 30.degree. C., 20 rpm (.eta.20 rpm) being 1 to 1.8 when the latter viscosity (.eta.20 rpm) is adjusted to 5,000 to 10,000 mPa.multidot.S.The aqueous emulsion according to the present invention is excellent in structural viscosity (flowability, high speed application performance), provides coated layers with high water resistance and low-temperature stability, and can be suitably used extensively as an adhesive for paper, wood and plastics, as a binder for impregnated paper and non-woven products, as an additive for mortar, as a paint, and in paper and fiber processings.Type: GrantFiled: March 21, 1995Date of Patent: February 4, 1997Assignee: Kuraray Co., Ltd.Inventors: Masato Nakamae, Naoki Fujiwara, Kazutoshi Terada, Daisuke Miyake, Ken Yuki, Toshiaki Sato, Hitoshi Maruyama
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Patent number: 5571860Abstract: An emulsion adhesion composition comprising a polyvinyl alcohol stabilized polymer emulsion; the polymer comprising 40 to 94.5% by weight of a vinyl ester of an C.sub.1 -C.sub.13 alkanoic acid, 5 to 40% by weight ethylene and 0.5 to 10% by weight N-vinyl formamide or N-vinyl pyrrolidone, the adhesive being characterized by superior adhesion and heat resistance.Type: GrantFiled: June 2, 1995Date of Patent: November 5, 1996Assignee: National Starch and Chemical Investment Holding CorporationInventors: Pravin K. Kukkala, Malcolm F. Hallam, M. Erin Jones, Richard K. Vetterl
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Patent number: 5563187Abstract: Aqueous emulsions of grafted polymer compositions are provided. The grafted component of these compositions has two or more polymeric substituents. The aqueous emulsions of grafted polymer compositions are particularly useful as cement modifiers.Type: GrantFiled: February 16, 1995Date of Patent: October 8, 1996Assignee: Rohm and Haas CompanyInventors: Shang J. Chiou, Miao-Hsun L. Sheng
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Patent number: 5496884Abstract: An adhesive composition containing a polyvinyl alcohol-stabilized butadiene polymer latex and a methylene donor compound. The butadiene polymer latex is prepared by an emulsion polymerization in the presence of polyvinyl alcohol. The adhesive composition may also contain other optional ingredients such as a supplemental polymeric film-forming component, a nitroso compound crosslinker, a maleimide compound crosslinker, a vulcanizing agent, and an acid-scavenging compound. The polyvinyl alcohol-stabilized butadiene polymer latex and methylene donor compound combine to provide a tightly crosslinked, robust film which provides for excellent adhesion and environmental resistance.Type: GrantFiled: November 12, 1993Date of Patent: March 5, 1996Assignee: Lord CorporationInventors: Mark A. Weih, Helmut W. Kucera, Patrick A. Warren, Douglas H. Mowrey
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Patent number: 5492960Abstract: A method of making polymeric particles of at least 1.0 micrometer which comprises forming at atmospheric conditions droplets of an ethylenically unsaturated monomer the monomer being liquid at standard conditions of 0.degree. C. and one atmosphere pressure, together with from about 0.01 to about 5 percent by weight, based on the weight of the monomer, of a nonreactive compound in an aqueous medium, the nonreactive compound having a solubility in water less than that of the ethylenically unsaturated monomer, the aqueous medium containing a surfactant or organic hydrophilic colloid, the monomer droplets being formed by using only sufficient energy to achieve a size of 1.0 micrometer or larger, and polymerizing the ethylenically unsaturated monomer.Type: GrantFiled: October 28, 1994Date of Patent: February 20, 1996Assignee: Eastman Kodak CompanyInventors: John L. Muehlbauer, Dennis E. Smith, Thomas H. Whitesides
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Patent number: 5480934Abstract: An aqueous, low-viscosity, water-soluble polymeric dispersion containing a polymer (A) is prepared by copolymerizing monomers:(a1) 99 to 70 weight % of at least one water-soluble monomer,(a2) 1 to 30 weight % of at least one hydrophobic monomer and,(a3) 0 to 20 weight % of at least one amphiphilic monomer, which monomers constitute 100 weight % of the polymers forming material which polymer (A) has an average molecular weight M.sub.W (mean weight) of at least 5.times.10.sup.5 Dalton, said process comprising:a first step i) of reacting said monomer ingredients in an aqueous dispersion in the presence of at least one polymeric dispersing agent (D) thereby preparing a dispersion of polymer (A); and a second step ii) of adding at least one polymeric dispersion agent (D), in an aqueous solution, to the dispersion.Type: GrantFiled: May 12, 1994Date of Patent: January 2, 1996Assignee: Roehm GmbH Chemische FabrikInventors: Bernfried Messner, Carl Joachim, Gunter Schmitt, Manfred Braum, Peter Quis
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Patent number: 5473006Abstract: The invention relates to polyvinyl alcohol-modified, rosin-based, resin-fortified emulsion polymer compositions having improved properties which are useful in formulating gravure and flexographic printing inks. Additionally, the invention relates to the method of preparing these emulsion polymer compositions.Type: GrantFiled: April 11, 1994Date of Patent: December 5, 1995Assignee: Westvaco CorporationInventors: G. Frederick Hutter, Paul J. Zuraw
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Patent number: 5473005Abstract: A water based thixotropic adhesive gel is disclosed which contains: water; polyvinyl alcohol, or wherein a portion of the polyvinyl alcohol is replaced with polyvinylpyrrolidone; xanthan gum to impart thixotropic properties to the gel; and a plasticizer for the polyvinyl alcohol. The gel has a thixotropic index which permits the viscosity of the adhesive to break down when a flexible tube or squeeze bottle dispenser is finger-pressed while having a sufficiently low viscosity to allow for easy extrusion from an orifice having a diameter of about 0.06 to 0.15 inches. When pressure is released, after the desired amount of adhesive has flown out of the dispenser, the adhesive quickly reverts to very close to its original gel state so that it does not run on a vertical surface of porous or semiporous material such as paper. Preferred gels contain a water soluble dye and are clear.Type: GrantFiled: February 9, 1994Date of Patent: December 5, 1995Assignee: Borden, Inc.Inventors: Peter S. Columbus, John Anderson, Yogeshbhai B. Patel
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Patent number: 5470903Abstract: A method for preparing aqueous polymer emulsions by effecting polymerization of vinyl monomers in the presence of a stabilizing amount of a water soluble poly(N-vinylformamide) containing polymer as a protective colloid and aqueous polymer emulsions containing poly(N-vinylformamide) stablizer.Type: GrantFiled: July 20, 1994Date of Patent: November 28, 1995Assignee: Air Products and Chemicals, Inc.Inventors: William E. Lenney, Dennis Sagl
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Patent number: 5447983Abstract: A method for producing a large size crosslinked polymer bead, which comprises dispersing a monomer phase composed essentially of a monovinyl monomer and a crosslinkable monomer in an aqueous phase containing a dispersion stabilizer and subjecting the dispersion to suspension polymerization in an oil-in-water system in the presence of a polymerization initiator, wherein: 1 at least one specific gravity-controlling agent having a specific gravity of more than 1.0 selected from the group consisting of water-insoluble inert organic solvents and water-insoluble linear polymers soluble in the monomer phase, is added to the monomer phase, and 2 if necessary, at least one specific gravity-controlling agent selected from the group consisting of water-soluble inorganic salts, is added to the aqueous phase, 3 to adjust the specific gravities (at 25.degree. C.) of the monomer phase and the aqueous phase in the ranges represented by the following formula (I):B-0.03<A<B+0.Type: GrantFiled: February 6, 1995Date of Patent: September 5, 1995Assignee: Mitsubishi Chemical CorporationInventors: Kiyoto Ando, Hiroshi Arataki
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Patent number: 5439960Abstract: A woodworking adhesive composition prepared by a two stage emulsion polymerization procedure wherein the first stage comprises the step of emulsion polymerizing vinyl acetate with 0.1 to 6% by weight of a post-crosslinking monomer in the presence of polyvinyl alcohol to produce a polyvinyl alcohol stabilized copolymer having a Tg within the range of +10.degree. to +40.degree. C. and containing no pre-crosslinking monomers and the second stage comprises the step of emulsion polymerizing methyl methacrylate to produce a methyl methacrylate homo- or copolymer containing at least 75% by weight methyl methacrylate and having a Tg within the range of +50.degree. to +120.degree. C., further characterized in that the ratio of the polymer produced in the first stage to the polymer produced in the second stage is within the range of 10:1 to 10:6 and wherein the first stage polymer and second stage monomer mixture are not equilibrated prior to the second stage polymerization.Type: GrantFiled: September 2, 1994Date of Patent: August 8, 1995Assignee: National Starch and Chemical Investment Holding CorporationInventors: Paul R. Mudge, George Hespe
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Patent number: 5434216Abstract: Water resistant emulsions for woodworking adhesives may be prepared using an emulsion polymer, the polymer being prepared in the presence of 1 to 2.5% by weight of 88% hydrolyzed polyvinyl alcohol and 1 to 4% by weight of 95-99.5% (or above) hydrolyzed polyvinyl alcohol.Type: GrantFiled: May 7, 1993Date of Patent: July 18, 1995Assignee: National Starch and Chemical Investment Holding CorporationInventors: Paul R. Mudge, Pravin K. Kukkala, John Walker
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Patent number: 5395880Abstract: The present invention provides a method which makes it possible to manufacture substantially spherical resin granules with a narrow grain size distribution by a simple operation. According to the present invention, there is provided a method of manufacturing resin granules with a grain diameter of 1.about.100 .mu.m and narrow grain size distribution by controlling the cloud point of polyvinyl alcohol and other water soluble polymers.Type: GrantFiled: October 28, 1992Date of Patent: March 7, 1995Assignee: Nippon Paint Co., Ltd.Inventors: Haruhiko Sato, Naoya Yabuuchi, Shinji Seo, Takehiro Ojima
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Patent number: 5391608Abstract: A woodworking adhesive composition prepared by a two stage emulsion polymerization procedure wherein the first stage comprises the step of emulsion polymerizing vinyl acetate with 0.1 to 6% by weight of a post-crosslinking monomer in the presence of polyvinyl alcohol to produce a polyvinyl alcohol stabilized copolymer having a Tg within the range of +10.degree. to +40.degree. C. and containing no pre-crosslinking monomers and the second stage comprises the step of emulsion polymerizing methyl methacrylate to produce a methyl methacrylate homo- or copolymer containing at least 75% by weight methyl methacrylate and having a Tg within the range of +50.degree. to +120.degree. C., further characterized in that the ratio of the polymer produced in the first stage to the polymer produced in the second stage is within the range of 10:1 to 10:6 and wherein the first stage polymer and second stage monomer mixture are not equilibrated prior to the second stage polymerization.Type: GrantFiled: September 3, 1993Date of Patent: February 21, 1995Assignee: National Starch and Chemical Investment Holding CorporationInventors: Paul R. Mudge, George Hespe
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Patent number: 5387638Abstract: There is disclosed an emulsion composition which comprises an aqueous emulsion (A) obtained by emulsion polymerization of 100 parts by weight of an ethylenically unsaturated monomer in the presence of 1 to 15 parts by weight of a carboxyl group-modified polyvinyl alcohol such as itaconic acid-modified polyvinyl alcohol as the dispersant and a polyamide resin (B) such as polyamide epichlorohydrin. The above emulsion composition has a long pot-life and can easily be made into a film having a high wet strength and being excellent in water resistance, hot water resistance and heat resistance. Accordingly, it can effectively be utilized in a variety of applications including paint coating, adhesive, fiber sizing agent and paper coating.Type: GrantFiled: August 25, 1993Date of Patent: February 7, 1995Assignee: Kuraray Co., Ltd.Inventors: Masato Nakamae, Ken Yuki, Hirotoshi Miyazaki, Hitoshi Maruyama
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Patent number: 5360860Abstract: A water-soluble resin emulsion comprising at least two incompatible water-soluble polymers, wherein said incompatible water-soluble polymers are stably compatibilized with each other by emulsion-polymerizing a monomer having a reactive unsaturated group in the presence of said incompatible water-soluble polymers as the protecting colloid. The emulsion is useful for a topcoating, prime-coating, material for a synthetic leather, photosensitive material for the preparation of a color filter, material for silver salt photography, and photosensitive material for screen printing.Type: GrantFiled: June 26, 1992Date of Patent: November 1, 1994Assignee: Oji Kako Co., Ltd.Inventors: Hiroshi Itoh, Naoki Isobe, Tadashi Asazuma
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Patent number: 5354803Abstract: A surfactantless, formaldehyde-free polyvinyl alcohol graft copolymer binder emulsion for non-woven products is prepared comprising: 12% to 35% of a fully hydrolyzed low or ultra low molecular weight PVOH and 65% to 88% of a vinyl and/or acrylic monomer which is graft copolymerized with the PVOH through emulsion polymerization.Type: GrantFiled: March 29, 1993Date of Patent: October 11, 1994Assignee: Sequa Chemicals, Inc.Inventors: Louis R. Dragner, William C. Floyd
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Patent number: 5349008Abstract: Disclosed herein is a process for suspension polymerization of a vinyl polymer which comprises using as the suspending agent a polyvinyl ester polymer having an ionic group at an end thereof or a polyvinyl alcohol polymer having a degree of hydrolysis of 90 mol % or less which is obtained by hydrolysis of the above polyvinyl ester polymer.According to the above-mentioned process, vinyl polymer granules having a sharp granulometric dispersion, high bulk density, high plasticizer absorption and low vinyl monomer residue are obtained.Type: GrantFiled: December 4, 1991Date of Patent: September 20, 1994Assignee: Kuraray Co., Ltd.Inventors: Shigeki Takada, Ken Yuki, Hitoshi Maruyama, Taku Tanaka, Kazunari Igarashi
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Patent number: 5326809Abstract: A method for preparing aqueous polymer emulsions in the presence of a poly[(vinyl alcohol)-co-(vinyl amine)] copolymer as a protective colloid and aqueous polymer emulsions containing a poly[(vinyl alcohol)-co-(vinyl amine)] copolymer.Type: GrantFiled: November 25, 1992Date of Patent: July 5, 1994Assignee: Air Products and Chemicals, Inc.Inventors: Richard H. Bott, William E. Lenney, Keith D. Campbell, Jeffrey A. Kuphal, Chung-Ling Mao
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Patent number: 5322880Abstract: A water based thixotropic adhesive gel is disclosed which consists essentially of: water; partially hydrolyzed polyvinyl alcohol, or wherein a portion of the polyvinyl alcohol is replaced with polyvinylpyrrolidone; a water-soluble high viscosity thickening agent polymer which is compatible with the polyvinyl alcohol and which imparts thixotropic properties to the gel; a water-soluble plasticizer for the polyvinyl alcohol; and a watersoluble defoamer in proportion of ingredients so that the viscosity of the adhesive will break down when a flexible tube or squeeze bottle dispenser is finger-pressed and have a sufficiently low viscosity to allow for easy extrusion from an orifice having a diameter of about 0.06 to 0.15 inches. When pressure is released, after the desired amount of adhesive has flown out of the dispenser, the adhesive quickly reverts to very close to its original gel state so that it will not run on a vertical surface on porous and semiporous surfaces such as paper.Type: GrantFiled: November 10, 1993Date of Patent: June 21, 1994Assignee: Borden, Inc.Inventors: Peter S. Columbus, John Anderson, Yogeshbhai B. Patel
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Patent number: 5319055Abstract: Novel thickening agents, useful for thickening non-aqueous solvent-containing compositions, are provided. The thickening agents are the reaction product of a polyol containing at least two hydroxyl groups; a polyisocyanate containing at least two isocyanato groups; and an active hydrogen compound. A method of thickening non-aqueous systems by admixing with the novel thickening agents is also provided.Type: GrantFiled: October 18, 1991Date of Patent: June 7, 1994Assignee: Rohm and Haas CompanyInventors: Peter R. Sperry, Chao-jen Chung
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Patent number: 5308910Abstract: There is disclosed a composition which comprises an aqueous emulsion selected from (A-1) aqueous emulsion comprising a dispersoid which comprises a vinyl ester polymer (1) and a copolymer a (meth)acrylic ester and a primary hydroxyl group-containing ethylenically unsaturated monomer (2), the polymer (1) being present principally in the central part of the dispersoid, the copolymer (2) having a glass transition temperature of lower than 50.degree. C. an being present principally in the peripheral part thereof; and a dispersant comprising a vinyl alcohol polymer and (A-2) aqueous emulsion comprising a dispersoid which comprises a copolymer of a hydrophobic unsaturated monomer such as (meth)acrylic ester and a primary hydroxyl group-containing ethylenically unsaturated monomer; and a dispersant comprising a vinyl alcohol polymer having a mercapto group at an end thereof and a (B) polyvalent isocyanate compound.Type: GrantFiled: June 24, 1992Date of Patent: May 3, 1994Assignee: Kuraray Co., Ltd.Inventors: Ken Yuki, Masato Nakamae, Hitoshi Maruyama, Tatsuaki Hattori
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Patent number: 5296532Abstract: The invention relates to adhesive compositions for gluing wood containing aqueous vinyl ester graft copolymer dispersions and water-soluble acid metal salts or free acids, in which the adhesive compositions exhibit outstanding resistance to hot water and have high storage stability. The vinyl ester graft copolymer comprises from 2 to 12 percent by weight, based on the total weight of the graft copolymer, of one or more polyvinyl alcohols having a degree of hydrolysis of from 60 to 99 mol persent and 88 to 98 percent by weight, based on the total weight of the graft copolymer, of a grafting monomer mixture. The grafting monomer mixture contains from 5 to 50 percent by weight, based on the total weight of the monomer mixture, of vinyl esters of saturated, highly branched aliphatic monocarboxylic acids having 9 or 10 carbon atoms, vinyl pivalate, diisopropyl maleate, diisopropyl fumarate, vinyl chloride and mixtures thereof.Type: GrantFiled: February 14, 1992Date of Patent: March 22, 1994Assignee: Wacker-Chemie GmbHInventors: Reinhard Haerzschel, Rudolf Weissgerber, Herbert Kaiser, Wilhelm Kaiser
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Patent number: 5284897Abstract: A water based thixotropic adhesive gel is disclosed which consists essentially of: water; partially hydrolyzed polyvinyl alcohol, or wherein a portion of the polyvinyl alcohol is replaced with polyvinylpyrrolidone; a water-soluble high viscosity thickening agent polymer which is compatible with the polyvinyl alcohol and which imparts thixotropic properties to the gel; a water-soluble plasticizer for the polyvinyl alcohol; and a watersoluble defoamer in proportion of ingredients so that the viscosity of the adhesive will break down when a flexible tube or squeeze bottle dispenser is finger-pressed and have a sufficiently low viscosity to allow for easy extrusion from an orifice having a diameter of about 0.06 to 0.15 inches. When pressure is released, after the desired amount of adhesive has flown out of the dispenser, the adhesive quickly reverts to very close to its original gel state so that it will not run on a vertical surface on porous and semiporous surfaces such as paper.Type: GrantFiled: November 16, 1992Date of Patent: February 8, 1994Assignee: Borden, Inc.Inventors: Peter S. Columbus, John Anderson, Yogeshbhai B. Patel
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Patent number: 5284900Abstract: The present invention yields a coating film excellent in adhesion, water resistance, solvent resistance and durability. A compound having a carboxyl group and a long-chain alkylthio group or a salt thereof is used as an emulsifier and emulsion polymerization is carried out using a polymerizable monomer or monomers having, within their molecule, a group reactive with a carboxyl group as raw materials for emulsion polymerization, whereby the resin produced by emulsion polymerization and the emulsifier react with each other efficiently on the occasion of film formation and form a crosslinked structure. When a compound having a polymerizable unsaturated group in addition to the carboxyl group and long-chain alkylthio group or a salt thereof is used as the emulsifier, not only the above-mentioned crosslinked structure is formed but also the polymerizable unsaturated group in the emulsifier will react with the unsaturated group in the polymerizable monomer or monomers in the manner of grafting.Type: GrantFiled: May 31, 1991Date of Patent: February 8, 1994Assignees: Nippon Shokubai Co., Ltd., Oji Paper Co., Ltd.Inventors: Masuji Izubayashi, Masatoshi Yoshida, Toshiaki Matsunaga, Kohei Hori, Teruo Kikuta, Shiro Nakano, Hidetoshi Hatta
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Patent number: 5278211Abstract: Formaldehyde free crosslinking emulsion polymers are prepared by the addition of N-(2,2-dialkoxy-1-hydroxy)ethyl acrylamide to a vinyl ester based polymer. The resultant emulsions can be used as binders for nonwovens or fiberfill or as woodworking adhesives.Type: GrantFiled: April 5, 1993Date of Patent: January 11, 1994Assignee: National Starch and Chemical Investment Holding CorporationInventors: Rama S. Chandran, Carmine P. Iovine, Paul R. Mudge, John C. Leighton, Pravin K. Kukkala
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Patent number: 5274057Abstract: An improved process for producing resin particles by a bead suspension polymerization reaction, and a polymer formed by the process wherein the process comprises: providing a liquid reaction medium suitable for conducting the polymerization; forming a suspension agent system in the reaction medium by an in situ interaction of at least two components in the reaction medium, for example, certain water soluble metal halides and polyvinylacetate derived polymers; adding at least one polymerizable monomer compound to the resulting reaction medium having the suspension agent system dispersed therein; and effecting polymerization of the monomer in the reaction medium to form low ash content beads of the polymer.Type: GrantFiled: December 23, 1991Date of Patent: December 28, 1993Assignee: Xerox CorporationInventors: Michael K. Georges, Robert D. Bayley, Lupu Alexandru
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Patent number: 5262466Abstract: A masking composition, which serves to prevent diffusion of one metal into selected areas of a substrate of another metal when said composition is applied to said selected areas, comprises a suspension of a masking powder in an aqueous solution comprising water and water soluble alcohol in which is dissolved polyvinyl alcohol.Type: GrantFiled: November 1, 1991Date of Patent: November 16, 1993Assignee: Alloy Surfaces Co. Inc.Inventor: Alfonso L. Baldi
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Patent number: 5248720Abstract: A process for preparing a polyamide composite material comprising (1) contacting a layered silicate having a cation exchange capacity of 50 to 200 milliequivalents/100 g with an organic cation of a lactam which is a swelling agent in a dispersing medium, thereby obtaining a composite having the organic cation of the lactam adsorbed onto the layered silicate, and mixing the composite with a polyamide monomer; or (2) mixing a layered silicate having a cation exchange capacity of 50 to 200 milliequivalents/100 g with a compound which becomes a swelling agent through the action of an acid, a polyamide monomer and acid with pKa value of 0 to 3 in a dispersing medium. The mixture containing the polyamide monomer is polymerized to prepare the polyamide composite material.Type: GrantFiled: February 6, 1992Date of Patent: September 28, 1993Assignees: Ube Industries, Ltd., Toyota Jidosha Kabushiki Kaisha, Kabushiki Kaisha Toyota Chuo KenkyushoInventors: Ryuichi Deguchi, Takeyoshi Nishio, Akane Okada
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Patent number: 5244737Abstract: Very small (100 nanometres maximum) non-ionically-stabilised core-sheath addition polymer particles, wherein the core is addition polymer and the sheath polyoxyalkylene chains, at least a portion of which chains are bonded to the core, there being present on each core sufficient chains such that the mass ratio of core to sheath is from 98:2 to 60:40. The particles are prepared by polymerisation in aqueous media initiated at under 40.degree. C. In a preferred embodiment, a seed-feed process is used. The dispersions exhibit excellent rheological characteristics and are useful, for example, as film-formers in coating compositions.Type: GrantFiled: June 10, 1992Date of Patent: September 14, 1993Assignee: ICI Australia Operations Proprietary LimitedInventors: Geoffrey B. Anderson, David S. Bignell, Iain B. Cook, Bruce Leary, Christopher J. Lyons
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Patent number: 5215682Abstract: Process for preparing a latex of polypyrrole in an aqueous reagent medium containing a ferric salt, a hydrolysed polyvinyl acetate and a dodecyl sulphate.The films prepared with this conducting latex are homogeneous, adhere to metals and metallized glasses and have high conductivity.Type: GrantFiled: August 29, 1991Date of Patent: June 1, 1993Assignee: Solvay S.A.Inventors: Elise Destryker, Etienne Hannecart
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Patent number: 5216065Abstract: A process for emulsion polymerization to form a latex having a particle size greater than about 0.5 micrometers by charging to a reaction vessel under agitation a reaction mixture including water, emulsifiers at an initial concentration slightly greater than or equal to the critical micelle concentration, a protective colloid, ethylenically unsaturated monomers, and an ionically balanced combination of an anionic and a cationic water soluble free radical initiator or a nonionic initiator; reacting the mixture to form an emulsion of polymerized monomer; and adding additional monomer, emulsifier, and protective colloid and a water soluble chain transfer agent to the reactor while continuing to agitate the mixture under conditions such that the emulsifier concentration does not exceed that at which new polymeric nuclei are formed.Type: GrantFiled: November 29, 1990Date of Patent: June 1, 1993Assignee: The Mead CorporationInventors: Emerson K. Colyer, Elizabeth A. B. Reno, Charles G. Ruffner, Jr., Rong-Chang Liang
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Patent number: 5200459Abstract: A butadiene heteropolymer latex is prepared by emulsion polymerizing appropriate monomers in the presence of polyvinyl alcohol and a stabilizing solvent. The butadiene heteropolymer can be a butadiene copolymer or terpolymer prepared from butadiene monomers and comonomers such as .alpha.-haloacrylonitrile and acrylic acid. The butadiene heteropolymer latices can be prepared without problems of coagulation and can be utilized effectively in adhesive compositions without the use of volatile solvents. Adhesive bonds prepared from the butadiene heteropolymer latices also avoid the side effect problems associated with polymers prepared utilizing conventional surfactant-based emulsion polymerization techniques.Type: GrantFiled: May 31, 1991Date of Patent: April 6, 1993Assignee: Lord CorporationInventors: Mark A. Weih, Helmut W. Kucera
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Patent number: 5182328Abstract: An aqueous vinyl acetate/N-methylolacrylate copolymer emulsion for RF curable Type I wood adhesive compositions prepared by the polymerization of vinyl acetate and N-methylolacrylamide in the presence of 1 to 5 wt% tetramethylol glycoluril and a stabilizing system consisting essentially of 3 to 5 wt% polyvinyl alcohol, the weight percentages being based upon vinyl acetate monomer.Type: GrantFiled: March 4, 1992Date of Patent: January 26, 1993Assignee: Air Products and Chemicals, Inc.Inventors: John G. Iacoveillo, David W. Horwat
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Patent number: 5143966Abstract: In a vinyl acetate-ethylene copolymer emulsion prepared by the aqueous emulsion copolymerization of vinyl acetate and ethylene in the presence of a polyvinyl alcohol stabilizing system, the improvement which comprises a vinyl acetate-ethylene copolymer emulsion prepared in the presence of a stabilizing system consisting essentially of:(a) 0.2 top 1.5 wt % low molecular weight, partially hydrolyzed polyvinyl alcohol,(b) 0.5 to 2.5 wt % medium molecular weight, partially hydrolyzed polyvinyl alcohol, and(c) 1 to 4 wt % medium molecular weight and/or high molecular weight, fully hydrolyzed polyvinyl alcohol,the weight percentages based on vinyl acetate monomer.Type: GrantFiled: November 7, 1990Date of Patent: September 1, 1992Assignee: Air Products and Chemicals, Inc.Inventors: Hsueh-Chi Lee, William E. Lenney
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Patent number: 5141814Abstract: Very small (100 nanometers maximum) non-ionically-stabilized core-sheath addition polymer particles, wherein the core is addition polymer and the sheath polyoxylkylene chains, at least a portion of which chains are bonded to the core, there being present on each core sufficient chains such that the mass ratio of core to sheath is from 98:2 to 60:40. The particles are prepared by polymerization in aqueous media initiated at under 40.degree. C. In a preferred embodiment, a seed-feed process is used. The dispersions exhibit excellent rheological characteristics and are useful, for example, as film-formers in coating compositions.Type: GrantFiled: March 23, 1990Date of Patent: August 25, 1992Assignee: ICI Australia Operations Proprietary Ltd.Inventors: Geoffrey B. Anderson, David S. Bignell, Iain B. Cook, Bruce Leary, Christopher J. Lyons
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Patent number: 5126392Abstract: A shade enhancing agent comprises an aqueous resin emulsion composition obtained by polymerizing a monomer in the presence of a cationic surfactant or a cationic protective colloid, polymerizing a monomer and adding a cationic protective colloid or polymerizing a monomer in the presence of a cationic or nonionic emulsifying dispersant so as to have a cationic group in the molecule, a dry film of said composition having a glass transition point (Tg) in the range between 20.degree. C. and 110.degree. C. and a refractive index of 1.50 or less, said emulsion composition having a zeta potential in the range between +5 and +80 mV at an ion strength of 10.sup.-3 and a pH value of 7.Type: GrantFiled: December 22, 1989Date of Patent: June 30, 1992Assignee: Kao CorporationInventors: Norihiko Nakashima, Yoshinobu Ishikawa, Akihiro Kondo, Masaki Tumadori
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Patent number: 5124394Abstract: A method for preparing an aqueous copolymer emulsion comprising the aqueous copolymerization of vinyl acetate and ethylene in the presence of a stabilizing system consisting essentially of a stabilizing effective amount of poly(ethyloxazoline).Type: GrantFiled: April 12, 1991Date of Patent: June 23, 1992Assignee: Air Products and Chemicals, Inc.Inventor: William E. Lenney
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Patent number: 5110856Abstract: A vinyl acetate-ethylene copolymer emulsion is disclosed, comprising a vinyl acetate-ethylene copolymer composed of from 10 to 40% by weight of an ethylene unit and from 90 to 60% by weight of a vinyl acetate unit and an emulsifying dispersant in an amount of from 2.5 parts by weight or more but less than 5.0 parts by weight per 100 parts by weight of the vinyl acetate unit, and having a mean particle size of not larger than 0.9 .mu.m and a solids content of from 65 to 75% by weight, wherein the emulsifying dispersant contains from 1.0 to 1.9 parts by weight of partially saponified polyvinyl alcohol prepared so as to have an average polymerization degree of from 300 to 1,000 and from 1.0 to 3.0 parts by weight of a polyoxyethylene nonionic surface active agent having an HLB of from 16.5 to 17.5 per 100 parts by weight of the vinyl acetate unit. A process for producing the vinyl acetate-ethylene copolymer is also disclosed.Type: GrantFiled: September 17, 1991Date of Patent: May 5, 1992Assignee: Sumitomo Chemical Co., Ltd.Inventors: Takeo Oyamada, Yoshito Taira, Masayoshi Nitta, Yasuo Kaneshima, Tateshi Kurino, Shizuo Narisawa
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Patent number: 5104914Abstract: It is the object of this invention to provide a method for the preparation of an antiblocking agent which is effective in its antiblocking activity but is considerable less visible in photographic enlargements made from the film containing the antiblock of this invention.There is described a process for the preparation of monodispersed polymer particles between 5 and 10 microns in diameter which comprises preparing a dispersion of monosized seed polymer particles and then adding to this dispersion an ethylenically unsaturated monomer which is different from the monomer used to prepare the seed polymer particles, together with a polymerization initiator and completing the polymerization, the refractive index of one of the polymers produced being greater than 1.54 and the refractive index of the other polymer being less than 1.54.The refractive index of gelatin is 1.54. There is produced by the process of the present invention a particle which comprises two polymers.Type: GrantFiled: May 10, 1990Date of Patent: April 14, 1992Assignee: Ilford LimitedInventors: Peter J. Elton, John L. Cawse
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Patent number: RE35144Abstract: A water based thixotropic adhesive gel is disclosed which consists essentially of: water; partially hydrolyzed polyvinyl alcohol, or wherein a portion of the polyvinyl alcohol is replaced with polyvinylpyrrolidone; a water-soluble high viscosity thickening agent polymer which is compatible with the polyvinyl alcohol and which imparts thixotropic properties to the gel; a water-soluble plasticizer for the polyvinyl alcohol; and a watersoluble defoamer in proportion of ingredients so that the viscosity of the adhesive will break down when a flexible tube or squeeze bottle dispenser is finger-pressed and have a sufficiently low viscosity to allow for easy extrusion from an orifice having a diameter of about 0.06 to 0.12 inches. When pressure is released, after the desired amount of adhesive has flown out of the dispenser, the adhesive quickly reverts to very close to its original gel state so that it will not run on a vertical surface on porous and semiporous surfaces such as paper.Type: GrantFiled: August 15, 1994Date of Patent: January 9, 1996Assignee: Borden, Inc.Inventors: Peter S. Columbus, John Anderson, Yogeshbhai B. Patel