US20150038625A1 - Monobenzoate useful as a plasticizer in adhesive preparations - Google Patents

Monobenzoate useful as a plasticizer in adhesive preparations Download PDF

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US20150038625A1
US20150038625A1 US14/378,563 US201314378563A US2015038625A1 US 20150038625 A1 US20150038625 A1 US 20150038625A1 US 201314378563 A US201314378563 A US 201314378563A US 2015038625 A1 US2015038625 A1 US 2015038625A1
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plasticizer
plasticizers
monobenzoate
adhesive
results
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William D. Arendt
Emily MCBRIDE
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Emerald Kalama Chemical LLC
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Emerald Kalama Chemical LLC
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Publication of US20150038625A1 publication Critical patent/US20150038625A1/en
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Assigned to EMERALD KALAMA CHEMICAL, LLC reassignment EMERALD KALAMA CHEMICAL, LLC RELEASE OF SECURITY INTEREST IN PATENTS - SECOND LIEN Assignors: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined

Definitions

  • 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.
  • 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.
  • Adhesives 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.
  • copolymers of ethylene and vinyl acetate are useful for adhesives.
  • Adhesives are formulated in both water (waterborne) and solvent-based (non-aqueous) systems.
  • 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.
  • Tg glass transition temperature
  • MFFT minimum film formation temperature
  • 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.
  • DEGDB diethylene glycol dibenzoate
  • DPGDB dipropylene glycol dibenzoate
  • TAGDB triethylene glycol dibenzoates
  • 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.
  • DEGDB dibenzoate plasticizers
  • DPGDB 1,2 propylene glycol dibenzoate
  • plasticizers useful for latex adhesives are the phthalates, i.e., benzyl phthalate (BBP), Di-n-butyl phthalate (DBP) and diisobutyl phthalate (DIBP).
  • BBP benzyl phthalate
  • DBP Di-n-butyl phthalate
  • DIBP diisobutyl phthalate
  • high solvating plasticizers useful in adhesive compositions include some glycols, citric acid esters, alkyl sulfonic acid esters, and certain phosphates.
  • 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.
  • 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.
  • 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.
  • migratory issues associated with the use of packaging adhesives.
  • plasticizer for use in adhesive applications, which is environmentally safe, non-hazardous and non-toxic in use.
  • 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.
  • 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).
  • MFFT water reduction and chalk point
  • 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.
  • This invention is directed to a non-phthalate monobenzoate plasticizer useful as a plasticizer for polymeric dispersions, such as adhesives.
  • 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.
  • PPB 3-phenyl propyl benzoate
  • the invention is a plasticizer useful for adhesive compositions comprising 3 PPB.
  • the invention is a waterborne adhesive composition
  • the inventive plasticizer including but not limited to waterborne latex glues and waterborne acrylics.
  • the invention is a caulk composition comprising the inventive plasticizer.
  • the invention is a sealant composition comprising the inventive plasticizer.
  • the invention is a non-aqueous based adhesive composition comprising the inventive plasticizer.
  • the invention is a blend of traditional plasticizers with the inventive plasticizer.
  • the invention relates to the use of the inventive plasticizer and adhesive compositions in applications.
  • 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.
  • 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.
  • FIG. 1 shows the volatility characteristics determined for the neat plasticizers evaluated, using the Oven Volatility test, one hour, at 110° C.
  • FIG. 2 shows the One Day Viscosity responses obtained in Pace® 383 polyvinyl acetate (PVAc homopolymer) at 10 wt. % of each of the plasticizers evaluated.
  • FIGS. 3 ( a ) and ( b ) show One Day Viscosity responses obtained in polyvinyl acetate ethylene (PVA/E) copolymers, Copolymer A (Elvace® 735) ( FIG. 3 ( a )) and Copolymer B (Vinnapas® 400) ( FIG. 3 ( b )), at 5 wt. % of each of the plasticizers evaluated.
  • PVA/E polyvinyl acetate ethylene
  • FIG. 4 shows water reduction results (to 2000 mPa's) of the PVAc homopolymer obtained at concentrations of 5, 10, 15 and 20 wt. % of each of the plasticizers evaluated.
  • FIGS. 5 ( a ) and ( b ) show water reduction results (to 2000 mPa's) of the two PVA/E copolymers, A and B, respectively, obtained at concentrations of 5, 10 and 15 wt. % of each of the plasticizers evaluated.
  • FIG. 6 reflects Tg results obtained for plasticizer concentrations of 5, 10, and 20 wt. % in PVAc homopolymer.
  • FIGS. 7 ( a ) and ( b ) reflect Tg results obtained for plasticizer concentrations of 5, 10, 15 and 20 wt. % in the two copolymers, A and B, respectively.
  • FIG. 8 shows set times obtained for the various plasticizers at 10 wt. % concentration in PVAc homopolymer.
  • FIGS. 9 ( a ) and ( b ) show set times obtained for the various plasticizers at wt. % concentration in copolymers A and B, respectively.
  • FIG. 10 shows open times obtained for the various plasticizers at 10 wt. % concentration in PVAc homopolymer.
  • FIGS. 11 ( a ) and ( b ) show open times obtained for the various plasticizers at 5 wt. % concentration in copolymers A and B, respectively.
  • FIGS. 12 ( a ) and ( b ) show peel strength results obtained for the various plasticizers at 5 wt. % concentration in PVA/E copolymer, dry and after one hour water soak, respectively, using the T-Peel Cotton to Cotton Test.
  • FIGS. 13 and 14 show initial and one day Brookfield Viscosity results, respectively, of PVAc homopolymer at concentrations of 5, 10, 15 and 20 wt. % of each of the plasticizers evaluated.
  • FIGS. 15 and 16 show three and seven day Brookfield Viscosity results, respectively, of PVAc homopolymer at concentrations of 5, 10, 15 and 20 wt. % of the each of the plasticizers evaluated.
  • FIGS. 17 and 18 show four week and eight week Brookfield Viscosity results, respectively, of PVAc homopolymer at concentrations of 5, 10, 15 and 20 wt. % of each of the plasticizers evaluated.
  • FIGS. 19 ( a ), ( b ), (c) and (d) show shear results of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 20 shows Tg results of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 21 shows set time results of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 22 shows open time results of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 23 shows results of the 180° cotton to acrylic peel test for PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 24 shows results of the second trial of the 180° cotton to acrylic peel test for PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of the plasticizers evaluated.
  • FIG. 25 shows a comparison of the results of the first trial and second trial 180° cotton to acrylic peel tests reflected in FIGS. 23 and 24 .
  • FIG. 26 shows the average of the results obtained for the 180° cotton to acrylic peel test reflected in FIGS. 23 and 24 .
  • FIG. 27 shows the results of the 180° cotton to flexible vinyl peel test for PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 28 shows the results of the dry T-Peel, cotton to cotton test for PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 29 shows the results of the water reduction (to 2000 mPa's) test for PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 30 shows the Hysteresis Loop (wet tack) results of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 31 shows the chalk point data of PVAc homopolymer at 5, 10, 15 and 20 wt. % concentrations of the plasticizers evaluated.
  • FIGS. 32 , 33 ( a ), 33 ( b ) and 34 show the initial, one, three and seven day Brookfield Viscosities, respectively, of Elvacee 735 copolymer formulations using plasticizer concentrations of 5, 10 and 15 wt. % of each of the plasticizers evaluated.
  • FIGS. 35 , 36 and 37 show shear results of Elvacee 735 copolymer formulations at 5, 10 and 15 wt. % plasticizer concentrations, respectively.
  • FIG. 38 shows Tg results of Elvacee 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 39 shows set time results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 40 shows open time results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 41 shows water reduction (to 2000 cP) of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 42 shows Hysteresis Loop (wet tack) results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 43 shows dry T-Peel, cotton to cotton, results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % concentrations of each of the plasticizers evaluated.
  • FIG. 44 shows T-Peel, cotton to cotton, results after a one hour water soak of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers evaluated.
  • FIG. 45 shows T-Peel cotton to cotton strength loss after a one hour water soak of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers evaluated.
  • FIG. 46 shows 180° Peel, Flexible PVC to Luan results of Elvacee 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers evaluated.
  • FIGS. 47 , 48 and 49 show the initial, one and three day Brookfield Viscosities, respectively, of Elvace® 735 copolymer formulations at 5, 10, and 15 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • FIGS. 50 , 51 and 52 show the initial, one and three day Brookfield viscosities, respectively, of Pace® 383 (PVAc) homopolymer formulations at 5, 10, 15 and 20 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • PVAc Pace® 383
  • FIG. 53 shows 1 week viscosity results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • FIG. 54 shows Tg results of Pace® 383 homopolymer formulations at 5, 10, 15 and 20 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • FIG. 55 shows Tg results of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • FIGS. 56 and 57 show set and open times, respectively, of Elvace® 735 copolymer formulations at 5, 10 and 15 wt. % of each of the plasticizers and plasticizer blends evaluated.
  • FIG. 58 shows initial viscosity measurements of a basic packaging glue at 10 phr (9 wt. %) concentrations of each of the plasticizers evaluated.
  • FIG. 59 shows water reduction (to 1500 mPa's) of a basic packaging glue at 10 phr (9 wt. %) concentrations of each of the plasticizers evaluated.
  • FIGS. 60 and 61 show set times, unreduced and water reduced, for Kraft to Kraft and Kraft to Mylar samples, respectively, of packaging glue at 10 phr (9 wt. %) concentrations of each of the plasticizers evaluated.
  • FIG. 62 shows open time results for unreduced and water reduced samples of a basic packaging glue at 10 phr (9 wt. %) concentrations of each of the plasticizers evaluated.
  • 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.
  • 3-PPB 3-phenyl propyl benzoate
  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • IOB isononyl benzoate
  • IB isodecyl benzoate
  • EHB 2-ethylhexyl benzoate
  • 2,2,4-trimethyl-1,3-pentanediol diisobutyrate can also be blended with the inventive monobenzoate.
  • 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.
  • 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.
  • PSA pressure sensitive adhesive
  • plasticizers were evaluated in 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.
  • plasticizers were selected for evaluation in the examples 1-9 (in whole or part):
  • 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.
  • Test Methodology Specific details of the test methods are described below:
  • 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.
  • 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.
  • FIG. 1 illustrates the volatility characteristics determined for the neat plasticizers evaluated. Except for triacetin, which is 100% volatile and 100% water soluble, the plasticizers of the evaluation were all low in volatility and, thus, would not contribute significantly to the overall VOC of an adhesive formulation at typical levels of use.
  • the inventive monobenzoate, 3 PPB was slightly more volatile than dibenzoate plasticizers, but still well within an acceptable range.
  • Viscosity response is indicative of the compatibility of the plasticizer with the polymer.
  • FIG. 2 illustrates the One Day viscosity response of the various plasticizers evaluated. All of the plasticizers showed comparable viscosity responses, reflecting compatibility with the base polymer.
  • FIGS. 3 ( a ) and 3 ( b ) show One Day viscosity responses with 5 wt. % plasticizer in PVA/E copolymers, both A and B. Again, the viscosity responses are comparable, reflecting good compatibility with the base polymer.
  • FIGS. 4 and 5 ( a ) and 5 ( b ) reflect the water reduction results, i.e., the amount of water required to get to the desired viscosity of 2000 mPa's for the homopolymer (PVAc) and copolymers (PVA/E, A & B), respectively, using plasticizer concentrations of 5, 10, 15 and 20 wt. % for the homopolymer and 5, 10 and 15 wt. % for the copolymers. The amount of water required in each was comparable among the plasticizers evaluated.
  • Tg Glass transition temperatures
  • FIGS. 7 ( a ) and 7 ( b ) reflect the Tg results for the copolymers A and B, respectively. While there was some variability between polymers, the inventive monobenzoate, 3-PPB, performed comparable to the dibenzoate plasticizers.
  • FIGS. 9 ( a ) and 9 ( b ) show that the inventive monobenzoate performed comparable to or slightly better than the dibenzoates in the copolymers and was equivalent to ATBC. Set time results demonstrate that the inventive monobenzoate reduces the bond formation time in the various polymeric adhesives.
  • FIG. 10 shows that the inventive monobenzoate achieved longer open times than the dibenzoate plasticizers and comparable to triacetin and ATBC in the homopolymer.
  • FIGS. 11 ( a ) and 11 ( b ) show that the inventive monobenzoate achieved longer open times than the other plasticizers in Copolymer A and equivalent open times with Copolymer B, respectively.
  • 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 FIGS. 12 a (dry) and 12 b (after one hour water soak) show that the inventive monobenzoate performed better than the dibenzoate blend and comparable to ATBC. After the one hour water soak, the inventive monobenzoate performed slightly better than 1,2-propylene glycol dibenzoate, the dibenzoate blend and ATBC.
  • Each plasticizer was evaluated at concentrations of 5, 10, 15 and 20 wt. %.
  • FIGS. 15 and 16 The three and seven day viscosities obtained are shown in FIGS. 15 and 16 .
  • the viscosities followed the trend set forth with the initial and one day viscosities, with no notable increase over this time period.
  • the four week viscosities of the Pace® samples are shown in FIG. 17
  • the eight week viscosities are shown in FIG. 18 .
  • FIG. 18 reflects that all of the viscosities had increased from the previous four week reading, indicating they were all stable.
  • 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 FIGS. 19 ( a ), ( b ), (c) and (d). All of the plasticizers had acceptable rheology and were fairly comparable.
  • 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 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.
  • FIG. 28 shows the results from the dry T-peel, cotton to cotton test for the Pace® homopolymer samples at 5, 10, 15 and 20 wt. % plasticizer concentrations. For most of the plasticizers, there was a climb in peel strength up to 10 wt. %, then a decline with increasing plasticizer concentration at 15 wt. % and 20 wt. %. The X-100 (PGDB) showed a good increase in peel strength at the higher levels. 3-PPB had good peel strength versus the other plasticizers at low levels of plasticizer concentration, although it weakened the adhesive when used at levels greater than 10%. This is predictable as it is very efficient in softening.
  • the water reduction results (to 2000 mPa's) of the Pace® homopolymer emulsions are shown in FIG. 29 .
  • the amounts of water necessary to reduce the emulsion viscosities down to 2000 cP are fairly comparable between the plasticizer types, which was expected due to the similar viscosity responses the emulsions originally had.
  • 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 ⁇ m, 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.
  • FIG. 30 shows the additional data for Paces homopolymer formulations.
  • 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 ⁇ m 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.
  • Each plasticizer was evaluated at concentrations of 5, 10, and 15 wt. %.
  • the initial, one and three day viscosities of the Elvace® copolymer emulsions are shown in FIGS. 32 and 33 ( a ) and ( b ), respectively.
  • the seven day viscosities of the Elvacee copolymer emulsions are shown in FIG. 34 .
  • the viscosities of all of the samples were comparable, with 3-PPB (X-613) and A-4 showing marginally better viscosity response over the dibenzoates.
  • Elvace® copolymer shears were run using the cone geometry in order to obtain optimal results.
  • the shear curves are shown in FIGS. 35 , 36 and 37 . All of the plasticizers were similar in their shear responses.
  • the Tg's of the Elvace® copolymer samples were measured, and the results are shown in FIG. 38 .
  • the Tg suppression of 3-PPB was very efficient and mirrored that of the A-4; both had substantial improvements in Tg suppression over the dibenzoates at all levels of test.
  • the hysteresis loop results for the Elvace® copolymer samples are shown in FIG. 42 .
  • the dibenzoates showed the best wet tack across all concentrations, while the performance of 3-PPB and A-4 were very similar to each other.
  • FIGS. 43 , 44 and 45 show the results of the water resistance T-Peel, cotton to cotton tests performed on the Elvace® copolymer samples. Both the dry peel strengths and the peel strength loss after water immersion were all fairly comparable between the samples, with perhaps a slight advantage in water resistance seen with the 5 wt. % and 10 wt. % 3-PPB (X-613) samples.
  • peel strength of the PVC to Luan of the Elvace® copolymer samples are shown in FIG. 46 . Peel strengths of all samples were comparable, with no notable increase in peel strength as the plasticizer level increased.
  • Plasticizers & Blends
  • FIGS. 47 , 48 and 49 show the initial, 1 and 3 day viscosities, respectively, for Elvace® copolymer samples.
  • the samples made with K-Flex® IB had very low initial viscosity, with a gradual build over time to values near those of the dibenzoates and blends.
  • the initial, one and three day viscosities of the Pace® homopolymer samples are shown in FIGS. 50 , 51 and 52 .
  • the IB formulations all of the samples showed good viscosity response.
  • the IB was equivalent, but at about 15-20 wt. % plasticizer concentration, the IB viscosity response started lagging behind the others.
  • FIG. 53 shows the 1 week viscosities for the Elvace® copolymer samples
  • the glass transition temperatures of the monobenzoate blends formulated with Pace® homopolymer are shown in FIG. 54 .
  • This figure shows the limited compatibility of K-Flex IB with this homopolymer. Even at only 5 wt. %, IB has the poorest Tg suppression of all of the plasticizers that were evaluated: as the IB concentration increases, the Tg stays the same, indicating its incompatibility.
  • FIG. 55 shows the Tg results with the Elvace® copolymer samples.
  • the IB actually showed a greater efficiency in reducing the Tg's of the copolymer than the K-Flex® 850S or the 3-PPB blends. This makes sense, as IB's low polarity should be more compatible with the ethylene blocks of the copolymer than the other di- and mono-benzoates.
  • the 50:50 X-100/X-613 showed similar Tg suppression to that of the DE blends.
  • FIGS. 56 and 57 show the set and open time of the Elvace® copolymer samples. Overall, the 75:25 X-100/X-613 samples showed the fastest set times. With the exception of the IB and the 50:50 K-Flex® DE:X-613 samples, all of the open times increased with increasing plasticizer level and all of the samples appeared to be equivalent.
  • FIG. 58 shows the initial viscosity measurements reflecting that the inventive monobenzoate, 3-PPB, has a slightly better effect on viscosity than the dibenzoates and comparable to DIBP, a phthalate plasticizer.
  • FIG. 59 shows the water reduction results (to 1500 mPa's) reflecting that 3-PPB has among the highest amount of water add back (among the non-phthalates) to achieve the desired viscosity reduction.
  • FIGS. 60 and 61 Set Times for Kraft to Kraft and Kraft to Mylar samples, respectively, unreduced and water reduced, are shown in FIGS. 60 and 61 .
  • the results reflect that in some instances the inventive monobenzoate enhanced the set time and in others performed comparably to other plasticizers.
  • inventive monobenzoate plasticizer 3 PPB
  • functions well in adhesives performing comparably or better than traditional plasticizers used in adhesives, including the dibenzoates.
  • inventive monobenzoate is an alternative to phthalate plasticizers and has the potential to improve upon the safety of plasticizer technology for the adhesive industry.

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