MONOBENZOATE USEFUL AS A PLASTICIZER IN ADHESIVE PREPARATIONS
A unique monobenzoate useful as a plasticizer in polymeric dispersions, such as adhesives, comprising 3-phenyl propyl benzoate, a monobenzoate ester used as a flavor and fragrance additive, but not heretofore utilized as a plasticizer for polymeric dispersions, such as adhesives, caulks and sealants. The inventive monobenzoate provides a suitable non-phthalate, lower VOC alternative plasticizer that is compatible with a wide variety of polymers. Advantages rendered by the use of the inventive monobenzoate include, among other things, excellent viscosity response, low viscosity, viscosity stability, improved rheology, good film formation and comparable or better adhesion, peel strength, set time, open time, chalk point and MFFT, compared with that achieved by traditional plasticizers. The inventive monobenzoate also has an excellent health, safety and environmental profile and provides a viable alternative for adhesives used in food contact applications, such as packaging, where migratory concerns are an issue.
This invention is directed to a monobenzoate found to be unexpectedly useful as a plasticizer in a variety of polymer applications, including but not limited to adhesives, caulks, sealants and the like. In particular, this invention is directed to the use of a monobenzoate ester, 3-phenyl propyl benzoate, in adhesive applications or adhesive products. The inventive monobenzoate has comparable or better rheology, viscosity stability, compatibility, processability, open time, set time, peel strength and water reduction, among other advantages, over traditional plasticizers. The invention is also directed to polymeric compositions comprising the inventive monobenzoate, such as water-based adhesives, non-aqueous based adhesives, caulks and sealants.
BACKGROUND OF THE INVENTIONAdhesives are widely used in a number of applications, including without limitation envelopes; labeling; bonding, sealing and assembly of components and other materials; remoistening; stenciling; laminating; packaging; electronics manufacturing; high speed adhesive application; construction; transportation and the like. Certain polymers or polymer blends are well known, useful adhesives. By way of example only, copolymers of ethylene and vinyl acetate are useful for adhesives.
Adhesives are formulated in both water (waterborne) and solvent-based (non-aqueous) systems. Generally, solvent-based adhesives work more predictably and effectively under a wide range of conditions. Water-based systems are substantially or entirely free of most inherent toxic and hazardous properties of solvents, but do not always work in less than ideal conditions. There is a need for water-based systems that perform better or equivalent to solvent-based adhesives.
Plasticizers have been used as additives in adhesive compositions for some time to modify physical properties of the adhesive and the polymer film formed by the dried adhesive. Plasticizers facilitate the formation of an adhesive bond and prevent failure of the bond after aging. Plasticizers soften the polymer and add flexibility to the adhesive bond, without adversely affecting the degree of adhesion, lower the glass transition temperature (Tg) of the adhesive film making the polymer more flexible and the glue more efficient, and enhance film formation by lowering the minimum film formation temperature (MFFT). Plasticizers may also act as a fluid carrier for the polymeric component.
In all applications, the plasticizer should be compatible at least partially with the base polymer. Plasticizers should possess chemical stability, non-flammability, low toxicity and low volatility. Finally, plasticizers should also be economically feasible.
Dibenzoate plasticizers, such as diethylene glycol dibenzoate (DEGDB) and dipropylene glycol dibenzoate (DPGDB), are well known as general purpose plasticizers for latex adhesive applications. Blends of dibenzoates are also known and available. A high polarity blend of DEGDB, DPGDB and triethylene glycol dibenzoates (TEGDB) is available. More recently, a new dibenzoate triblend, comprising a blend of three dibenzoate plasticizers, DEGDB, DPGDB and 1,2 propylene glycol dibenzoate (PGDB), in various ratios, was introduced as a lower VOC plasticizer/coalescent alternative for use in plastisols, adhesives, coatings, and polishes, among other polymer applications.
Other plasticizers useful for latex adhesives are the phthalates, i.e., benzyl phthalate (BBP), Di-n-butyl phthalate (DBP) and diisobutyl phthalate (DIBP). Although not necessarily high solvating polar plasticizers, other examples of non-phthalate, high solvating plasticizers useful in adhesive compositions include some glycols, citric acid esters, alkyl sulfonic acid esters, and certain phosphates.
In addition to the dibenzoates discussed above, monobenzoates known to be useful as plasticizers include: isodecyl benzoate, isononyl benzoate, and 2-ethylhexyl benzoate. Isodecyl benzoate has been described as a useful coalescent agent for paint compositions and for use in the preparation of plastisols in U.S. Pat. No. 5,236,987 to Arendt. The use of isodecyl benzoate has also been described in U.S. Pat. No. 7,629,413 to Godwin et al. as a useful secondary plasticizer in combination with phthalate plasticizers for PVC plastisols. The use of 2-ethylhexyl benzoate in a blend with DEGDB and diethylene glycol monobenzoate is described in U.S. Pat. No. 6,989,830 to Arendt et al. The use of isononyl esters of benzoic acid as film-forming agents in compositions such as emulsion paints, mortars, plasters, adhesives, and varnishes is described in U.S. Pat. No. 7,638,569 to Grass et al.
“Half ester” monobenzoates include dipropylene glycol monobenzoate and diethylene glycol monobenzoate, which are byproducts of the production of dibenzoates, but which, most of the time, are not objects of production. Half esters are compatible with emulsions polymers, such as acrylic and/or vinyl ester polymers.
There remains a need for non-phthalate, lower VOC plasticizers for use in adhesive applications as alternatives to traditional plasticizers. Non-phthalate alternatives are particularly desirable in view of environmental, health and safety issues associated with many of the traditional plasticizers. In particular, in the food packaging industry, there is increasing concern for migratory issues associated with the use of packaging adhesives. There is, therefore, a need for a plasticizer for use in adhesive applications, which is environmentally safe, non-hazardous and non-toxic in use.
It has been discovered that an entirely different monobenzoate, 3-phenyl propyl benzoate (3 PPB), is a surprisingly effective lower VOC plasticizer alternative to other monobenzoates and certain phthalates for use in adhesives, caulks and sealants. Advantages of this monobenzoate are its excellent health, safety and environmental profile and handling properties, which are better than most dibenzoates and monobenzoates previously used. This new monobenzoate is not classified as hazardous under any hazard class, and no hazard labeling elements are required.
The monobenzoate, 3 PPB, has not been utilized in polymeric applications of the type discussed herein in the past. It has been used and continues to be used in flavoring and fragrance applications, making it an ideal candidate in applications where there are migratory concerns. It has also been used as a solubilizer for certain active or functional organic compounds in personal care products as described in U.S. Patent Publication 2005/0152858.
It is an object of the invention to provide an alternative non-phthalate plasticizer having excellent compatibility with a wide variety of polymers, with improved handling and a superior toxicological profile over traditional plasticizers, for use alone or in combination with other plasticizers in adhesive applications.
Yet another object of the invention is to provide a monobenzoate, 3 PPB, useful as a plasticizer in polymeric dispersions such as adhesives, which achieves comparable or better performance properties over traditional plasticizers, including but not limited to viscosity response, Tg suppression, set time, open time, peel strength, water reduction and chalk point (MFFT).
Still another object of the invention is to provide waterborne or non-aqueous adhesive compositions comprising the inventive monobenzoate having comparable or better properties than adhesive compositions utilizing traditional plasticizers.
A further object of the invention is to provide other inventive compositions comprising the inventive monobenzoate, including but not limited to caulks and sealants, for use in a wide variety of applications.
Other objects of the invention will be apparent from the description herein.
SUMMARY OF THE INVENTIONThis invention is directed to a non-phthalate monobenzoate plasticizer useful as a plasticizer for polymeric dispersions, such as adhesives. In particular, the invention is directed to the use of 3-phenyl propyl benzoate (3 PPB), a component not previously known or used as a plasticizer for polymeric adhesive compositions.
In one embodiment, the invention is a plasticizer useful for adhesive compositions comprising 3 PPB.
In a second embodiment, the invention is a waterborne adhesive composition comprising the inventive plasticizer, including but not limited to waterborne latex glues and waterborne acrylics.
In a third embodiment, the invention is a caulk composition comprising the inventive plasticizer.
In a fourth embodiment, the invention is a sealant composition comprising the inventive plasticizer.
In a fifth embodiment, the invention is a non-aqueous based adhesive composition comprising the inventive plasticizer.
In a sixth embodiment, the invention is a blend of traditional plasticizers with the inventive plasticizer.
In still other embodiments, the invention relates to the use of the inventive plasticizer and adhesive compositions in applications.
Use of the inventive monobenzoate in the same or similar amounts as traditional plasticizers results in comparable or better performance and handling properties than that achieved with traditional plasticizers. The inventive monobenzoate is non-toxic, as is evident by its past and continued use as a flavor and fragrance additive. As such, it does not have the environmental, health and safety issues associated with traditional plasticizers.
The present invention is directed to a unique monobenzoate plasticizer useful for a variety of applications as a primary or secondary plasticizer in adhesive applications. The unique monobenzoate comprises 3-phenyl propyl benzoate (3-PPB), a known flavor and fragrance compound, not previously known or used as a plasticizer for polymer-based adhesives, glues, sealants and caulks. The invention is also directed to adhesive, glue, sealant and caulk compositions comprising the inventive monobenzoate.
The inventive monobenzoate plasticizer can generally be utilized alone as a primary plasticizer or in blends with other plasticizers. Any of the known polymers that can be formulated into an adhesive can be used in combination with novel monobenzoate to prepare a lower VOC content, environmentally safe and non-hazardous composition in accordance with the present invention. The inventive monobenzoate may be particularly useful in food packaging applications where migration of the adhesive may be an issue.
Polymers useful to prepare the polymeric dispersions discussed herein are known in the art. The inventive composition is expected to be useful with a wide variety of polymers, including both waterborne and non-aqueous polymer compositions. Suitable waterborne polymers, include, but are not limited to, homopolymers and/or copolymers of: acrylics, polyvinyl acetate, vinyl acetate ethylene, polyacrylates, methacrylates, styrene acrylates, polychloroprenes, polyurethanes, and nitriles. Non-aqueous based polymers useful with the inventive monobenzoate include: acrylics, polyvinyl acetates, vinyl acetate ethylene, methacrylates, styrene acrylates, polychloroprenes, thermoplastic polyurethanes, polysulfides, aminos, epoxies, and polyamides. Use of the inventive 3-PPB plasticizer is not limited to any particular polymer, and the foregoing listing is not intended to be limiting of the invention. Other polymer-based compositions useful in adhesive applications and requiring plasticizers will be known to one skilled in the art.
The novel monobenzoate of the present invention may be used as a substitute or alternative plasticizer for various traditional adhesive polymer dispersions. A typical packaging adhesive is set forth below:
The inventive 3-PPB plasticizer is particularly useful for waterborne latex glues, including those comprising natural rubber latex and synthetic latex like polymers, waterborne acrylics, and non-aqueous adhesive compositions. In addition, the inventive 3-PPB plasticizer may also be used in caulks and sealants, so called “filled” adhesives. Dibenzoate esters are known to function well in these “filled” adhesives. Dibenzoate esters have a lower VOC content than 3-PPB; however, for these types of applications, the levels of VOC's associated with 3-PPB may be acceptable. The performance of 3-PPB is predictable in these applications based upon its performance with the polar polymers used in the adhesive market, as demonstrated by the examples.
The total amount of 3-PPB used in any particular polymeric dispersion would range broadly depending on the particular polymer, the characteristics of the polymer and other components, the process, the application or use and the results desired. By way of example only, in adhesives, plasticizers range in amounts from about 1 to about 50 wt. %, preferably from about 5 to about 20 wt. %, based on the weight of the wet adhesive. Preferred embodiments for an adhesive include 10 wt. % in homopolymer polyvinyl acetate and 5 wt. % in vinyl acetate ethylene copolymers. As a general rule, the harder the polymer (higher Tg), the more plasticizer required.
Useful amounts of 3 PPB are set forth in the examples. It is expected that one skilled in the art would be able to arrive at additional acceptable amounts based on the intended use and desired performance in the particular polymeric application.
The inventive 3-PPB plasticizer be, but is not required to be, blended with various other conventional plasticizers to enhance or augment properties of the adhesive compositions. Conventional plasticizers have been described herein and include, but are not limited to, phthalate esters up to C5, phosphate esters up to C4, adipates, citrates, succinates, isobutyrates, alkyl glycol esters, terephthalate esters, such as DBTP, 1,2-cyclohexane dicarboxylate esters, polyesters, alkyl glycol derivatives, sulfonamides, sulfonic acid esters, and benzoates, both mono- and di-benzoates.
Monobenzoates, such as isononyl benzoate (INB), isodecyl benzoate (IB), and 2-ethylhexyl benzoate (EHB), and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, can also be blended with the inventive monobenzoate.
The inventive monobenzoate may also combined with or include various amounts of conventional additives such as surfactants, thickeners, biocides, fillers, polyvinyl alcohol, defoamers, humectants and the like.
The inventive monobenzoate provides comparable or better compatibility, viscosity stability and response, rheology, water reduction, set time, open time, peel strength, adhesion, Tg suppression, and chalk point (MFFT), among other advantages. In many instances, the inventive monobenzoate outperforms industry standard plasticizers, regardless of VOC content, including traditional and newer dibenzoate blends. The monobenzoate is particularly useful as a plasticizer when considering the use of harder polymers as alternatives to softer polymers in a variety of low VOC formulations.
The inventive monobenzoate, 3-PPB, may be used in adhesive compositions, sealants and caulks for a large variety of applications. Example applications include packaging glues, adhesive assembly, labeling, laminates, envelopes, food packaging, wood glue, construction adhesives, transportation product assembly, electronic product assembly and pressure sensitive adhesive (PSA) applications, although this list is by no means exhaustive. Still other uses will be evident to one skilled in the adhesives art.
The invention is further described by the examples set forth herein.
EXAMPLESThe evaluation of the plasticizers consisted of a variety of experiments. First, VOC's of the neat plasticizers selected were determined. Then, effectiveness and efficiency of the plasticizers with basic polymeric compositions were determined versus established plasticizers.
The following polymers were utilized in the evaluation formulations: Pace® 383 polyvinyl acetate (PVAc), PVOH protected, homopolymer, and polyvinyl acetate/ethylene copolymers (PVA/E), 0° C. Tg, PVOH protected, from two suppliers designated “A” and “B”. The “A” copolymer is Elvace® 735 from Forbo, the “B” copolymer is Wacker's Vinnapas®400.
The following plasticizers were selected for evaluation in the examples 1-9 (in whole or part):
-
- K-Flex® PG (X 100)—1, 2 propylene glycol dibenzoate (PGDB)
- X 613—the inventive monobenzoate, 3-PPB
- K-Flex® 975 P—a next generation dibenzoate triblend comprising DEGDB, DPGDB and PGDB in specified proportions (80 wt. % of a 4:1 DEGDB:DPGDB and 20 wt. % PGDB)
- K-Flex® 850 S—a commercial diblend of diethylene glycol and dipropylene glycol dibenzoates (DEG/DPG DB)
- Benzoflex™ 2088—a competitive dibenzoate plasticizer blend (TEG/DEG/DPG dibenzoate)
- Diisobutyl phthalate (DIBP)
- Triacetin
- Acetylated tributyl citrate (ATBC) (Citroflex® A4), a well-known plasticizer for food contact polymer applications, adhesives, inks and vinyl
Plasticizers were utilized in various levels in the examples. For PVAc, 5, 10, 15 and 20 wt. % levels were used, based on wet adhesive weight. For PVA/E, both A and B, 5, 10 and 15 wt. % levels were used, based on wet adhesive weight.
Tests Utilized—The following tests were employed:
-
- On neat plasticizers—EPA 24, ASTM D2369 volatility, 110° C. for one hour; and a TGA isothermal scan at 110° C.
- On adhesives:
- Viscosity Response
- Tg suppression
- Water Reduction
- Set and Open Times
- T-Peel adhesion
Test Methodology—Specific details of the test methods are described below:
Volatility: ASTM D2369 used. A TGA isothermal for one hour under air at 110° C. was also employed.
Viscosity Response: Viscosity measurements were made using a Brookfield RVT at 20 RPM's for 10 revolutions at 23±2° C. The Brookfield viscosity was tested using the RVDVII+Pro Viscometer.
Tg Suppression: DSC Glass Transition Method: 10 mil (wet) films were drawn down on glass and left to dry overnight. After 24 hours, the films were removed from the plates and approximately 10 mg were placed in a closed aluminum DSC pan. The temperature was equilibrated at −75° C., then ramped at 5° C./min to 65° C. Glass transition was measured as the onset of Tg.
Water Reduction: 200 grams of plasticized polymer were weighed into 8 oz. jars. Small increments of water were added and viscosity was measured after each addition until the viscosity reached 2000+/−80 cP.
Set Time: Set time determinations were made using two strips of 50 lb. unbleached Kraft paper measuring 1″×14″ (top) and 1.5″×14″ (bottom). A small amount of adhesive was applied to the bottom strip, and a #20 wire wound rod metered the adhesive onto the bottom strip while a #16 wire wound rod (rubber banded to the #20) simultaneously pressed down the top strip. A timer was then immediately started and the strips were pulled apart until significant force was required to tear apart the strips and fiber tear was noted. Time at this point was recorded as the set time. A minimum of three repetitions were performed. Evaluations were performed blind.
Open time: A 1.5″×14″ piece of 50 lb. unbleached Kraft paper was placed on a glass surface, with a 1″×14″ piece of Kraft clipped to its top, rolled back so that the bottom piece was left uncovered. The top piece was sandwiched between a #0 and #14 wire wound rod with the #0 on top. A small amount of adhesive was applied to the top of the bottom strip and a #20 wire wound rod metered out the adhesive over the entire strip. A timer was started, and at a specified time interval (with intervals of 5 seconds) the top strip was laminated to the bottom using the #0 rod. The strips were then peeled apart and assessed for adhesion and fiber tear. This process was repeated until a specific time interval was confirmed in duplicate as the last time interval to result in significant fiber tear/adhesion. Evaluations were performed blind.
T-Peel Adhesion: The methodology for various peel adhesion tests is further described in connection with Examples 7 and 8.
Example 1 VOC/Volatility of Neat PlasticizersThe viscosity response of a Pace® 383 homopolymer (PVAc) adhesive composition with 10 wt. % plasticizer was evaluated. Viscosity response is indicative of the compatibility of the plasticizer with the polymer.
Glass transition temperatures (Tg) were obtained for plasticizer concentrations of 5, 10, 15 and 20 wt. % in homopolymer (PVAc) and for plasticizer concentrations of 5, 10 and 15 wt. % for the copolymers.
Set Times for the various plasticizers were evaluated in the homopolymer and both copolymers. Homopolymer evaluations were conducted with 10 wt. % plasticizer levels. Copolymer evaluations (both A and B) were conducted with 5 wt. % plasticizer levels. All of the plasticizers decreased the set time of the adhesives as expected.
The inventive monobenzoate performed very well in comparison with the other plasticizers in the homopolymer, as reflected in
Open Times for the various plasticizers were evaluated in the homopolymer and both copolymers. Homopolymer evaluations were conducted with 10 wt. % plasticizer. Copolymer evaluations were conducted with 5 wt. % plasticizer levels. All of the plasticizers increased the open time as compared to the blank control, which is desirable in certain adhesive applications.
This test provides a method for determining the water resistance of an adhesive by measuring its peel strength dry and its peel strength retention after one hour of immersion in water.
Samples were prepared by first drawing down some emulsion on a 6″×13″ cotton cloth using a #10 wire wound rod, at which time a timer was started. At the end of 60 seconds, a second amount of emulsion was applied using the 4 mil side of an 8 path applicator. At the end of an additional 60 seconds, the cloth was folded over on itself and pressed twice using a rolling pin. The specimens were then allowed to dry for a minimum of 24 hours. Two 1″ specimens were cut from each sample and each labeled A, B, etc. A minimum of 2 (most had 4) specimens were prepared per sample. The dry samples were pulled on the tensile tester at a rate of 12″/min. The corresponding set of wet samples was soaked in water for one hour before being pulled on the tensile tester.
The peel strength required to pull apart the bond between two cotton samples was determined on dry samples and after a one hour water soak for a PVA/E copolymer composition having 5 wt. % plasticizer. The inventive monobenzoate was compared against 1,2-propylene glycol, a dibenzoate blend, and ATBC. The results in
In the following examples 8-11, the efficacy of the inventive monobenzoate, 3-PPB (X-613), was evaluated in the identified adhesive formulations, comparing it against K-Flex® 850S (DEGDB/DPGDB) as the standard, Citroflex® A-4 (ATBC), and 1,2-propylene glycol dibenzoate (X-100, PGDB). Test methodologies are as described above. Methodologies for the additional tests conducted in these examples are set forth below.
Example 8 Pace® 383 (PVAc) Homopolymer FormulationEach plasticizer was evaluated at concentrations of 5, 10, 15 and 20 wt. %.
Brookfield Viscosity
The initial and one day Brookfield Viscosity results are shown in
The three and seven day viscosities obtained are shown in
Shear
AR2000 Shear Method: A 40 mm 1° steel cone geometry with Peltier plate was used. A dime sized amount of emulsion was placed on the Peltier plate. The shear ramp was run at 25° C. from 0 to 2500 s−1 over one minute. The results of the shear testing are shown in
Glass Transition
The Tg results are shown in
Set Time
The results of the set time are shown in
Open Time
The results of the open time testing on the Pace® samples are shown in
Tensile—180° Peel, Cotton to Acrylic Coated 3B Leneta Charts
180° Peel, Cotton to Acrylic Coated 3B Leneta Charts Method: 1″×14″ cotton strips were laminated to Leneta 3B acrylic coated charts using a #20 wire wound rod to draw down the emulsion and one pass of a rolling pin. The cotton was pulled at a 180° angle from the 3B chart at 12″/min. The data was averaged between 1″ and 5″ of the pull. Five specimens of each sample were run. Data was adjusted to remove slack from the results.
The results from the 180° cotton to acrylic peel are shown in
The 180° peel of cotton to acrylic coated 3B Leneta charts was repeated to confirm the enhanced adhesion noted with the 3-PPB samples. This time, six specimens of each sample were run. The samples formulated with 3-PPB showed greatly improved adhesion to the acrylic coating than the other plasticizers that were evaluated, with peel strengths of about twice the amount of the others. In fact, the break sensitivity had to be turned down for the method, as the tensile tester several times thought it detected a break with the 15 wt. % and 20 wt. % 3-PPB due to the large build-up of adhesion and ensuing release.
The mode of loss for all of the 180° peels was adhesive, and primarily occurred with all of the adhesive still adhered to the cotton strips. However, several of the 15 wt. % and 20 wt. % 3-PPB specimens, as well as in minor amounts with one 20 wt. % A-4 and one 20 wt. % K-Flex® 850S, had adhesive loss to the cotton, where the adhesive remained.
As described above, two trials were conducted for the cotton to acrylic 180° peel resulting in two sets of data, which showed similar trends. The data obtained for the first and second set of samples were averaged and are shown in
Tensile—180° Peel, Cotton to Flexible Vinyl
The cotton to flexible vinyl 180° peels were performed on the Pace® homopolymer samples. Once again, the results in
Tensile—T-Peel, Water Resistance, Cotton to Cotton
The methodology for this test is described in example 7, above.
The data from this set had good agreement from specimen to specimen (standard deviations of 0-23%).
Water Reduction
The water reduction results (to 2000 mPa's) of the Pace® homopolymer emulsions are shown in
Hysteresis Loop/Wet Tack
Hysteresis Loop Method: Hysteresis loop data was obtained on an AR-2000 using 20 mm steel plate geometry on a Peltier base plate at 20° C. The gap was set at 200 μm, then a small (nickel sized) amount of sample was sheared up to 1500 s−1 and back down within one minute. Samples were tested in triplicate using a fresh specimen for each measurement.
All of the wet tack data followed the expected trend, with an increase in wet tack as the plasticizer concentrations increased; however, some of the standard deviations were greater than 25%, and so additional data was gathered on those samples in order to obtain a better average.
MFFT—Chalk Point
Chalk Point Method: A sheet of aluminum foil was taped tightly over the MFFT plate and wiped down with acetone. The desired temperature range was chosen and the MFFT-90 was turned on. Cooling water was turned on, as well as an air flow of 4 L/min. The plate was left to equilibrate (about 30 minutes). A U-shaped film was drawn down using the 75 μm applicator cube. All three samples were drawn down within 10 minutes. The cover was then closed and the instrument was left to run for a minimum of an hour. The samples were then examined for chalk point and photos were taken.
The chalk points of the homopolymer adhesives were determined, and the results can be seen in
Each plasticizer was evaluated at concentrations of 5, 10, and 15 wt. %.
Brookfield Viscosity
The initial, one and three day viscosities of the Elvace® copolymer emulsions are shown in
Shear
Elvace® copolymer shears were run using the cone geometry in order to obtain optimal results. The shear curves are shown in
Glass Transition Temperature (Tg)
The Tg's of the Elvace® copolymer samples were measured, and the results are shown in
Set Time
The set time results for the Elvace® copolymer samples are shown in
Open Time
The open times of the Elvace® copolymer samples were measured, and the results are shown in
Water Reduction
The viscosities of portions of the Elvace® copolymer samples were reduced to 2000 cP with water. The results of the water reduction are shown in
Hysteresis Loop
The hysteresis loop results for the Elvace® copolymer samples are shown in
T-Peel, Water Resistance, Cotton to Cotton
180° Peel, Flexible PVC to Luan
180° Peel, Flexible PVC to Luan Sample Preparation: 1″×14″ strips of flexible, 12 mil thick PVC were laminated to 6″×10″ pieces of Luan plywood. The adhesive was applied using a #50 wire wound rod, and four strips were laminated to each piece of wood. Gentle pressure using a rolling pin, followed by finger pressure to wet out the PVC strips, was used to press the pieces together.
180° Peel, Flexible PVC to Luan Method: The PVC strips were pulled from the Luan at 12″/min. over 8″. The average peel strength was determined by the data obtained between 2″ and 7″.
The peel strength of the PVC to Luan of the Elvace® copolymer samples are shown in
Due to the good adhesion results for 3-PPB (X-613) obtained in the above example, new blends of 3-PPB with K-Flex® DE (DEGDB) and K-Flex® PG (PGDB, X-100) were put through a basic evaluation, along with K-Flex® IB, to provide a baseline of how typical monobenzoates behave. Samples evaluated included: 5, 10, 15 and 20 wt. % plasticizer concentrations in Pace® homopolymer, and 5, 10 and 15 wt. % plasticizer concentrations in Elvace® copolymer, using the plasticizers and blends of plasticizers listed below:
Plasticizers & Blends:
25% X-613 (3-PPB)/75% X-100 (PGDB)
50% X-613/50% X-100
25% X-613/75% K-Flex DE (DEGDB)
50% X-613150% K-Flex DE
K-Flex® IB (isodecyl benzoate)
K-Flex® 850S (DEGDB/DPGDB diblend)
Brookfield Viscosities
The initial, one and three day viscosities of the Pace® homopolymer samples are shown in
Glass Transition Temperature
The glass transition temperatures of the monobenzoate blends formulated with Pace® homopolymer are shown in
As would be expected, due to their relative efficiencies, the 3-PPB blends with K-Flex® DE showed the greatest Tg suppression, while the blends with X-100 (PGDB) showed slightly less Tg suppression.
Set and Open Time
The following example show the efficacy of the inventive monobenzoate with a basic packaging adhesive formulation described below:
Evaluations were performed comparing the inventive monobenzoate, 3-PPB, to PGDB (X 100), K-Flex® 850S (DEGDB/DPGDB diblend), Benzoflex® 2088 (TEG/DEG/DPG dibenzoate blend), and DIBP.
Set Times for Kraft to Kraft and Kraft to Mylar samples, respectively, unreduced and water reduced, are shown in
Open Time results for unreduced and water reduced samples are shown in
The foregoing examples reflect that the inventive monobenzoate plasticizer, 3 PPB, functions well in adhesives, performing comparably or better than traditional plasticizers used in adhesives, including the dibenzoates. The inventive monobenzoate is an alternative to phthalate plasticizers and has the potential to improve upon the safety of plasticizer technology for the adhesive industry.
In accordance with the patent statutes, the best mode and preferred embodiments have been set forth; the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
Claims
1. A monobenzoate plasticizer for use in polymeric compositions, comprising 3-phenyl propyl benzoate.
2. An adhesive composition comprising:
- a. a polymeric dispersion; and
- b. a plasticizer that is 3-phenyl propyl benzoate,
- wherein the 3-phenyl propyl benzoate is used to provide viscosity response, improved open and set times, MFFT, and Tg suppression and facilitates formation of the adhesive bond, whether used alone as a primary plasticizer or as a secondary plasticizer in combination with other traditional plasticizers.
3. The plasticizer as set forth in claim 1, wherein the polymeric composition is waterborne latex glue.
4. The plasticizer as set forth in claim 1, wherein the polymeric composition is a caulk composition.
5. The plasticizer composition of claim 1, wherein the polymeric composition is a sealant composition.
6. The adhesive composition of claim 2,
- wherein the polymeric dispersion is waterborne and the polymer is selected from the group consisting of waterborne acrylics, polyvinyl acetate, vinyl acetate ethylene, methacrylates, styrene acrylates, polychloroprenes, polyurethanes, and nitriles.
7. The adhesive composition of claim 2, wherein the polymeric dispersion is non-aqueous and the polymer is selected from the group consisting of acrylics, polyvinyl acetate, vinyl acetate ethylene, methacrylate, styrene acrylate, polychloroprenes, thermoplastic polyurethanes, polysulfides, aminos, epoxies and polyamides.
8. A plasticizer comprising a blend of 3-phenyl propyl benzoate in combination with other plasticizers comprising: phthalate plasticizers up to C5, phosphate esters up to C4, terephthalates, polyesters, citrates, adipates, succinates, 1,2-cyclohexane dicarboxylate esters, isobutyrates, alkyl glycol esters, sulfonamides, sulfonic acid esters, benzoates, or mixtures thereof.
9. A plasticizer comprising a blend of 3-phenyl propyl benzoate in combination with other plasticizers comprising: isononyl benzoate, isodecyl benzoate, 2-ethyl hexyl benzoate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or mixtures thereof.
10. (canceled)
11. A method of providing viscosity response, improved open and set times, Tg suppression and formation of the adhesive bond in adhesive formulations, comprising:
- a. adding a plasticizer that is 3-phenyl propyl benzoate to a polymeric dispersion.
Type: Application
Filed: Feb 14, 2013
Publication Date: Feb 5, 2015
Inventors: William D. Arendt (Libertyville, IL), Emily McBride (Kalama, WA)
Application Number: 14/378,563
International Classification: C08K 5/101 (20060101); C09J 131/04 (20060101);