WO1992019691A1 - Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons - Google Patents

Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons Download PDF

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Publication number
WO1992019691A1
WO1992019691A1 PCT/US1991/002879 US9102879W WO9219691A1 WO 1992019691 A1 WO1992019691 A1 WO 1992019691A1 US 9102879 W US9102879 W US 9102879W WO 9219691 A1 WO9219691 A1 WO 9219691A1
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WO
WIPO (PCT)
Prior art keywords
pressure
emulsion
sensitive adhesive
monomer
polymer
Prior art date
Application number
PCT/US1991/002879
Other languages
English (en)
Inventor
Prakash Mallya
Sebastian S. Plamthottam
Yehuda Ozari
Original Assignee
Avery Dennison Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Avery Dennison Corporation filed Critical Avery Dennison Corporation
Priority to CA002085989A priority Critical patent/CA2085989A1/fr
Priority to JP3509147A priority patent/JPH06501273A/ja
Priority to AU77933/91A priority patent/AU662481B2/en
Priority to PCT/US1991/002879 priority patent/WO1992019691A1/fr
Priority to EP91908970A priority patent/EP0536146B1/fr
Priority to DE69130707T priority patent/DE69130707T2/de
Priority claimed from CA002085989A external-priority patent/CA2085989A1/fr
Publication of WO1992019691A1 publication Critical patent/WO1992019691A1/fr

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Classifications

    • 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
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention is directed to electron beam or EB curing of emulsion-based pressure-sensitive adhesives to provide a pressure-sensitive adhesive with superior elevated temperature shear properties.
  • Emulsion polymers can be coated onto a substrate, e.g. face material, release liner, and/or a transfer surface, and a pressure-sensitive adhesive layer formed upon water evaporation.
  • emulsion pressure-sensitive adhesive compositions curable on exposure to electron-beam (EB) radiation to form adhesives having increased elevated temperature shear properties without a significant change in ambient temperature properties.
  • the adhesives are formed of one or more polymers having a glass transition temperature of at least 20oC below the use temperature. They may be branched emulsion polymers polymerized at temperatures of at least about 30°C, and predominantly linear emulsion polymers polymerized at a temperature less than about 20oC, and mixtures thereof.
  • the emulsion polymers are independently formed in emulsion of at least one first monomer which, when homopolymerized, has a glass transition temperature less than about 0°C and at least one second monomer which, when homopolymerized, has a glass transition temperature greater than about 0°C.
  • a multifunctional additive is provided to aid cure of branched polymers and benefits all emulsion systems.
  • Multifunctional additives are preferably present in an amount up to about 10% by weight based on the weight of the emulsion-polymers. If employed, the multifunctional additive is preferably present in a concentration of from about 0.2 to about 5% by weight of the emulsion polymer while presently preferred multifunctional additives consist of pentaerythritol triacrylate, trimethylolpropane trimethacrylate, and 1,6-hexanediol diacrylate, and mixtures thereof.
  • Cure is achieved at EB dosages up to about 100 kiloGray (kGy) preferably from about 5 to about 50 kGy.
  • pressure-sensitive adhesives having 180° peel in excess of about 250 N/m and a loop tack in excess of about 200 N/m while achieving a 70°C shear of at least 10 kiloseconds normally in excess of 86 kiloseconds.
  • Shear values at 100°C in excess of 10 kiloseconds and surprisingly in excess of 86 kiloseconds can also be achieved.
  • elevated temperature shear 70°C and 100°C may be increased several fold.
  • Acrylic-based emulsion polymers are preferred.
  • the preferred polymers have a storage modulus (C) of from about 3.2 ⁇ 10 4 Pa to about 1.2 ⁇ 10 5 Pa at a frequency of 10 -1 s -1 and from about 1.4 ⁇ 10 5 Pa to about 5.2 ⁇ 10 5 Pa at a frequency of 10 2 s -1 and a loss modulus (G") of from about 9.5 ⁇ 10 3 Pa to about 3.1 ⁇ 10 4 Pa at a frequency of 10 -1 s -1 and about 7 ⁇ 10 4 Pa to about 5.6 ⁇ 10 5 Pa at a frequency of 10 2 s -1 .
  • C storage modulus
  • G loss modulus
  • Acrylic emulsion polymers are preferably formed of about 50 to about 95% by weight of a first monomer which when homopolymerized has a glass transition temperature less than about -25°C and at least one second monomer which when homopolymerized has a glass transition temperature greater than about -25°C.
  • emulsion pressure-sensitive adhesives preferably acrylic-based pressure-sensitive adhesives
  • the emulsion pressure-sensitive adhesives are prepared in a conventional manner and modified by the addition of multifunctional additives and after coating onto a suitable substrate, electron-beam (EB) cured at dosage levels sufficient to increase elevated temperature adhesive performance.
  • Dosage levels employed are up to about 100 kiloGray (kGy) preferably from about 5 to about 50 kGy.
  • dosages as low as 10 kiloGray can enable a realization of and increase the 70°C shear from 0.4 kilosecond to an excess of 86 kiloseconds at a minimal loss of ambient temperature properties such as 180° peel and loop tack.
  • the pressure-sensitive adhesives preferably provided in accordance with the instant invention have a glass transition temperature at least about 20°C to about 70°C below use temperature and rheology wherein storage modulus (G') and loss modulus (G") are respectively in the range of about:
  • Emulsion-based pressure-sensitive adhesive polymers for use in the invention may be prepared in accordance with the present invention by copolymerizing monomers to yield a polymer having a glass transition temperature from about 20oC to about 70°C below use temperature preferably from about 50°C to about 70°C below use temperature.
  • solids content will generally range from about 40 to about 60% by weight solid's.
  • Catalysts such as tertiary butyl hydropero ⁇ ide or the like may be present in an amount of from about 0.15 to about 0.5 part by weight per 100 parts monomers with surfactant levels ranging from about 0.5% to about 5% by weight based on weight of the monomers.
  • Reaction temperature, catalyst content and surfactant levels control the nature of the polymer formed. While not bound by theory, elevated reaction temperatures, e.g. temperatures of about 30°C or more, tend to yield polymers which are more branched than polymers synthesized at lower temperatures.
  • branched polymer means a polymer emulsion synthesized at a temperature above about 30°C and is not normally responsive to the action of EB-radiation in the absence of a multifunctional monomer; while the term “linear polymer” means a polymer emulsion synthesized at a temperature below about 25°C and responsive to the action of EB radiation without the addition of a multifunctional additive.
  • branched polymers may be situations where a pendant group(s) of the monomers leading to the polymer are reactive and/or where the surfactant employed is reactive with the monomers and/or polymer.
  • Reactive surfactants are those based on C 7 -C 16 unsaturated fatty acids.
  • multifunctional additive an additive having 2 or more pendant functional groups, preferably acrylate or methacrylate groups.
  • PETA pentaerythritol triacrylate
  • TMPTMA trimethylolpropanetrimethacrylate
  • multifunctional additives having ethoxylated and propoxylated backbones may also be effectively used. As indicated, concentrations will vary depending on polymer nature and electron-beam dosage levels.
  • multifunctional additive concentrations can range from 0 to about 10% or more by weight of the emulsion polymer. None is required for highly linear polymers. Their presence is however beneficial. Blends of linear and branched polymers need multifunctional additives corresponding to the level of branched polymer in the mixture. A presently preferred range is from about 0.2 to about 5% by weight based on the weight of the polymers. While not bound by theory, a possible explanation for the beneficial use of multifunctional additives is that they may have a plasticizing effect on high gel content of branched emulsion polymers, i.e. polymers prepared at temperatures of about 30oC or more. Because of high gel content, diffusion of polymer chains between neighboring particles may be restricted.
  • emulsion polymers prepared in accordance with the present invention must have a net effective glass-transition temperature of from about 20° to about 70°C below the use temperature, preferably from about 50° to about 70°C below the use temperature.
  • the monomers used in the preparation of polymers of the instant invention are proportioned to provide polymerization products falling within the designated glass-transition temperature. It is for this reason that the first monomers, preferably one or more alkyl acrylates, are provided as the bulk of the monomers employed and are typically present in an amount of from about 50 to about 95 percent by weight based on the total weight of the monomers. It is also desired that they have pendant acrylate or methacrylate groups to enhance EB cure.
  • the emulsions formed including added multifunctional additives are coated on any suitable substrate such as face stock, release liner stock or transfer surfaces by means known in the art.
  • Net solids coating weights generally range from about 40 or less to about 60 grams or more per square meter.
  • Electron-beam dosages may range from about 10 kiloGray (kGy) or less up to about 100 kGy preferably 50 kGy or less depending on the nature of the polymer and amount of multifunctional additives present, with required dosages being lowered by the presence of a multifunctional additive.
  • the presence of a multifunctional additive can also create a limit on the EB dosages used. A peak is reached at some level after which the level of increase of elevated temperature shear will be reduced but still be above the level which existed prior to cure.
  • aqueous solution was made up by dissolving 0.6 gram of hydrosulfite AWC in 150 grams of deionized water.
  • the reactor mixture was purged with nitrogen, cooled to 5°C, and the pre-emulsion and aqueous solution feeds were started simultaneously.
  • the pre-emulsion was added over 2.5 hours, aqueous solution over 2.75 hours, temperature being maintained between 5 and 8oC.
  • the contents were held at 5oC for 2 more hours, discharged (after filtering through cheesecloth) and neutralized to a pH of 7.2 with NH 3 .
  • the total coagulum was 1.0 gram, the solids content of the emulsion was 38.9%, and the particle size was 139 nm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La polymérisation par faisceau d'électrons est utilisée seule ou en combinaison avec des additifs multi-fonctionnels afin d'améliorer la résistance au cisaillement à haute température d'adhésifs de contact polymérisés en émulsion.
PCT/US1991/002879 1991-04-26 1991-04-26 Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons WO1992019691A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002085989A CA2085989A1 (fr) 1991-04-26 1991-04-26 Adhesifs autocollants polymerises par emulsion chauffes par faisceau electronique
JP3509147A JPH06501273A (ja) 1991-04-26 1991-04-26 電子ビーム硬化されたエマルション系感圧粘着剤
AU77933/91A AU662481B2 (en) 1991-04-26 1991-04-26 Electron-beam cured emulsion pressure-sensitive adhesives
PCT/US1991/002879 WO1992019691A1 (fr) 1991-04-26 1991-04-26 Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons
EP91908970A EP0536146B1 (fr) 1991-04-26 1991-04-26 Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons
DE69130707T DE69130707T2 (de) 1991-04-26 1991-04-26 Elektronenstrahl gehärtete druckempfindliche klebstoffe auf emulsionsbasis

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA002085989A CA2085989A1 (fr) 1991-04-26 1991-04-26 Adhesifs autocollants polymerises par emulsion chauffes par faisceau electronique
PCT/US1991/002879 WO1992019691A1 (fr) 1991-04-26 1991-04-26 Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons

Publications (1)

Publication Number Publication Date
WO1992019691A1 true WO1992019691A1 (fr) 1992-11-12

Family

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Application Number Title Priority Date Filing Date
PCT/US1991/002879 WO1992019691A1 (fr) 1991-04-26 1991-04-26 Adhesifs de contact a base d'emulsion polymerisee par faisceau d'electrons

Country Status (2)

Country Link
JP (1) JPH06501273A (fr)
WO (1) WO1992019691A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544643B1 (en) 2000-09-26 2003-04-08 3M Innovative Properties Company Pressure sensitive adhesive comprising poly(1-alkene) elastomer and multifunctional (meth)acrylate, articles prepared therefrom and a method of making

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52121054A (en) * 1976-04-05 1977-10-12 Japan Atom Energy Res Inst Modification of aqueous polymer emulsion
US4101493A (en) * 1975-07-17 1978-07-18 Toagosei Chemical Industry Co., Ltd. Crosslinking emulsion
JPS6092372A (ja) * 1983-10-25 1985-05-23 Nitto Electric Ind Co Ltd エマルジヨン型感圧性接着剤の製造方法
JPS61103908A (ja) * 1984-10-26 1986-05-22 Nitto Electric Ind Co Ltd エマルジヨン型光硬化性粘着剤の製造方法
US4714655A (en) * 1985-10-04 1987-12-22 Avery International Corporation Pressure-sensitive adhesive containing heat-sensitive materials, and method of making the same
US4786552A (en) * 1986-07-07 1988-11-22 Avery International Corporation Curable arcylic/fumaric pressure-sensitive adhesives
US5011867A (en) * 1987-09-28 1991-04-30 Avery International Corporation Electron-beam cured emulsion pressure-sensitive adhesives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101493A (en) * 1975-07-17 1978-07-18 Toagosei Chemical Industry Co., Ltd. Crosslinking emulsion
JPS52121054A (en) * 1976-04-05 1977-10-12 Japan Atom Energy Res Inst Modification of aqueous polymer emulsion
JPS6092372A (ja) * 1983-10-25 1985-05-23 Nitto Electric Ind Co Ltd エマルジヨン型感圧性接着剤の製造方法
JPS61103908A (ja) * 1984-10-26 1986-05-22 Nitto Electric Ind Co Ltd エマルジヨン型光硬化性粘着剤の製造方法
US4714655A (en) * 1985-10-04 1987-12-22 Avery International Corporation Pressure-sensitive adhesive containing heat-sensitive materials, and method of making the same
US4786552A (en) * 1986-07-07 1988-11-22 Avery International Corporation Curable arcylic/fumaric pressure-sensitive adhesives
US5011867A (en) * 1987-09-28 1991-04-30 Avery International Corporation Electron-beam cured emulsion pressure-sensitive adhesives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0536146A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544643B1 (en) 2000-09-26 2003-04-08 3M Innovative Properties Company Pressure sensitive adhesive comprising poly(1-alkene) elastomer and multifunctional (meth)acrylate, articles prepared therefrom and a method of making

Also Published As

Publication number Publication date
JPH06501273A (ja) 1994-02-10

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