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WO1993009152A1 - Adhesifs autocollants thermofusibles durcissant par rayonnement ultraviolet - Google Patents

Adhesifs autocollants thermofusibles durcissant par rayonnement ultraviolet Download PDF

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Publication number
WO1993009152A1
WO1993009152A1 PCT/US1992/009493 US9209493W WO9309152A1 WO 1993009152 A1 WO1993009152 A1 WO 1993009152A1 US 9209493 W US9209493 W US 9209493W WO 9309152 A1 WO9309152 A1 WO 9309152A1
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Prior art keywords
recited
pressure
sensitive
monomers
adhesive copolymer
Prior art date
Application number
PCT/US1992/009493
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English (en)
Inventor
Tjoan Liem Ang
Original Assignee
Avery Dennison Corporation
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Priority to CA002122921A priority Critical patent/CA2122921A1/fr
Publication of WO1993009152A1 publication Critical patent/WO1993009152A1/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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • This invention is related to photo-curable, pressure-sensitive adhesives.
  • PSAs High-performance pressure-sensitive adhesives
  • PSAs are normally characterized by the ability of the adhesive to withstand creep or shear deformation at high loadings and/or high temperatures while exhibiting adequate tack and peel adhesion proper ⁇ ties.
  • This balance of properties is derived from the polymer structure of the PSA.
  • Such polymers are characterized by a high-molecular weight to provide the necessary resistance to shear deformation and by a low modulus of elasticity of the polymer backbone to allow the polymer to conform to a substrate surface upon contact. Certain surface energy and polarity requirements must also be satisfied for a good bond to form between the adhesive and the substrate.
  • the desired high molecular weights can be obtained either by primary polymerization of monomers to form long-chain-length backbones, or by crosslink- ing of pre-existing primary polymer chains.
  • the PSA polymer backbone should consist of material of low enough modulus or high enough compli ⁇ ance to make a good contact with the adherent at the application temperature. This condition is normally satisfied by the use of material of low glass-transi ⁇ tion temperatures (Tg's) , such as polymers or copoly- mers of 2-ethyl-hexylacrylate, iso-octylacrylate, butylacrylate, ethylacrylate, methylacrylate, or the like.
  • Tg's glass-transi ⁇ tion temperatures
  • Resistance to creep or shear deformation in a high-performance PSA is normally the result of a high internal cohesive strength.
  • This condition can usually be obtained from a high primary polymer molecular weight.
  • high internal cohesive strength can also be obtained by incorporating, into the polymer body, a high degree of interchain hydrogen bonding, ionic associa ⁇ tion, or covalent crosslinking.
  • crosslinking the adhesive by radiation after coating is one of the preferred methods of incorporating high cohesive strength.
  • the conversion of a fluid which flows and coats out well, into a non-flowing viscoelastic material can be done with better control by radiation crosslinking than by thermochemical means.
  • the polymer In order for a polymer to be crosslinkable by UV radiation, the polymer needs to carry vinyl unsaturation which, in the presence of small amounts of added multi-vinyl-functional monomers and a photoinitiator, would respond to vinyl addition polymerization upon UV radiation.
  • the combination of vinyl unsaturation on the polymer and multi-vinyl- functional monomers leads to very poor melt pot lives; polymer gelation in only an hour at the melt temperature is not uncommon with hot melt PSA formu ⁇ lations.
  • Crosslinking by UV radiation of a polymer without vinyl unsaturation is also possible when a peroxy compound is present in addition to the multi- vinyl-functional monomer and photoinitiator.
  • Peroxy compounds which have been used are benzoylperoxide and t-butylperbenzoate.
  • the pot lives of the unfunctionalized hot melt polymer in the presence of the peroxy compound and multi-vinyl- functional monomers are very short, i.e., of the order of an hour at the melt temperature.
  • U.S. Patent No. 4,181,752 discloses the manufac- ture of PSAs in web polymerization of a polymer- monomer syrup by UV irradiation.
  • the UV energy of 300 and 400 nm wavelength is supplied at low intensities, 0.001 to 0.070 k atts/m 2 while maintaining the web temperature below 35°C.
  • the low UV intensity requirement necessitates that cure takes place at relatively low web speeds of about 2 inches per minute to 2 feet per minute.
  • this irradia- tion is preferably carried out under anaerobic conditions thus requiring an atmosphere control syste .
  • U.S. Patent No. 4,052,527 discloses a method of production of UV crosslinkable hot melt pressure-sensitive adhesives which contain photoinitiators of the 3-(chlorinated aryloxy)-2-hydroxypropyl acrylates or methacrylates.
  • the photoinitiators were copoly- merized into acrylic polymers and which contained other modifying monomers such as vinylics, and were made in solution, emulsion, or in bulk.
  • the solvent medium is vacuum-stripped so that the polymer can be coated as a melt between 120°C and 180°C. UV cure is obtained from commercial medium-pressure lamps of 200 Watts per inch intensi ⁇ ty.
  • U.S. Patent No. 4,144,157 and DE 27-43-979 discloses the UV crosslinkability of acrylic pres ⁇ sure-sensitive adhesives which were exemplified by polymers which are made in and coated out of solu ⁇ tion, or when made in bulk are to be coated out of solution.
  • the pressure-sensitive-adhesive materials are UV-cross- linkable to high shear strengths, because of copolymerizable photoinitiators in the pressure-sensitive adhesive polymer which belong to a class of (2-alkoxy,2-phenyl-2-benzoyl)ethyl 2- acrylates or methacrylates and the acrylate or methacrylate of benzoin or its derivative.
  • the UV cure is obtained by radiation from high-pressure mercury lamps or burners, with very-high-intensity outputs of from one lamp of 900 Watts to four lamps of 2000 Watts each.
  • the pressure-sensi ⁇ tive-adhesive material needs relatively high UV dosages of at least about 10 kJ/m 2 before high shear strengths can be obtained in the adhesive.
  • reactive crosslinking agents such as multifunctional acrylic monomers to the pressure- sensitive-adhesive material prior to coating and UV cure is explicitly discouraged to prevent poor shelf stability of the coater-ready material.
  • U.S. Patent No. 4,281,152 describes the synthe ⁇ sis of benzophenone derivatives which are copolymeri- zable into a polymer backbone by way of acrylic functional groups.
  • the benzophenone derivatives are useful as a component in UV-curable resin composi ⁇ tions and in anaerobic thermosetting adhesive compo ⁇ sitions.
  • U.S. Patent No. 4,281,152 describes the synthe ⁇ sis of benzophenone derivatives which are copolymeri- zable into a polymer backbone by way of acrylic functional groups.
  • the benzophenone derivatives are useful as a component in UV-curable resin composi ⁇ tions and in anaerobic thermosetting adhesive compo ⁇ sitions.
  • 4,672,079 describes a method of manufacturing polystyrene derivatives with UV- activatable functional groups, and the use of these compounds in the photopolymerization of monomer or oligomer mixtures with ethylenic unsaturation for use in wood .paints, paper lacquers, printing inks, engraving printed and integrated circuits, fabric printing, and the like, but not for pressure-sensi ⁇ tive adhesives.
  • European Patent Application No. 87-304396.2 and U.S. Patent No. 4,737,559 describe the synthesis and the use of benzophenone and acetophenone photo ⁇ initiator derivatives, which are coplymerizable into a copolymer backbone by acrylic or acrylamide func ⁇ tional groups for use in adhesive compositions for human skin contact application.
  • a pressure-sensitive adhesive is described which is a copolymer of acrylic monomers and the ketone derivative, by means of which the copolymer can be UV-crosslinked.
  • the present invention relates to a pressure- sensitive-adhesive copolymer comprising at least one copolymerizable photoinitiator monomer, at least one low-glass-transition-temperature monomer, and at least one multifunctional monomer and to a process for preparing such polymers.
  • the actinic radiation cure of the polymer is performed with light at about 240 to about 410 nm wavelength, light intensity of about 6 to about 10 kWatts/m 2 , and temperature of about 45°C to about 125°C, under aerobic conditions.
  • the resultant pressure-sensitive adhesives exhibit cohesive strength and high-temperature shear strength which, when put to a static shear test, do not fail after several thousand minutes; tack performance of about 300 to about 500 N/m; peel adhesion performance of about 550 to about 650 N/m; a shelf-life at room temperature of more than about 10 months, with no increase in the viscosity of the polymer; and a hot- melt pot-life at 100°C of at least 10 days, with little or substantially no increase in the viscosity of the polymer.
  • coplymerizable photoinitiator monomers for use in the present invention are selected from the group consisting of benzoin compounds, acyloin compounds, and mixtures thereof, and, in a preferred embodiment of the invention, are selected from the group consisting of DAROCUR ZLI 3331 and DAROCUR 2959.
  • the multifunctional monomers for use in the present invention are selected from the group con ⁇ sisting of diethy leneglyco ldiacry late , triethyleneglycoldiacrylate , tr ipropyleneglycol- diacrylate, 1 , 6 -hexaned i o Id i a cry 1 a t e , trimethylolpropanetriacrylate , tr imethylolpropanetr i- methacrylate, pentaerythritoltriacrylate, and mix ⁇ tures thereof.
  • the low-glass-transition-temperature monomers for use in the present invention are selected from the group consisting of 2-ethylhexylacrylate, iso- octylacrylate, butylacrylate, and mixtures thereof.
  • FIG. 1 is a graph of looptrack vs UV dosage for polymer-2.
  • FIG. 2 is a graph of peel adhesion vs. UV dosage for polymer-2.
  • FIG. 3 is a graph of melt viscosity at 100°C vs heating period at 100°C for polymer-4.
  • the present invention relates to high-perfor ⁇ mance, UV-cured, essentially acrylic-based, pressure- sensitive adhesives which can be in the form of hot melts, solution adhesive compositions, or emulsion adhesives, and to methods for their manufacture.
  • the adhesive polymer compositions comprise low Tgmonomers, such as 2-ethylhexylacrylate, iso-octyl- acrylate, butylacrylate, or the like.
  • the low Tg monomer is present in an amount of from about 40% to about 60% by weight.
  • monomers are incorporated to modify the polarity and the rheological and surface properties of the polymer, such as acrylic acid, methacrylic acid, maleic acid, jS-carboxyethyl- acrylate, esters of methacrylic acid, laurylacrylate, stearylacrylate, styrene, vinyltoluene, dibutylfumarate, dioctylmaleate, dioctylfumarate, vinylacetate, or the like. These monomers are present in an amount of from about 10% to about 40% by weight.
  • the adhesive polymer contains a copolymerizable photoinitiator sold under the trade name "DAROCUR ZLI 3331” by E. Merck of Darmstadt, Germany, and which is 4 (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2- « propyl)ketone.
  • the acryloyl group makes the molecule copolymerizable with other acrylic and vinylic monomers which make up the body of the adhesive polymer.
  • the photoinitiator activity of DAROCUR ZLI 3331 resides in the phenyl(2-hydroxy-2-propyl) etone moiety of the molecule.
  • a compound with this latter structure is sold under the trade name "DAROCUR 1173" by E. Merck.
  • DAROCUR 2959 An additional, related photoinitiator sold under the trade name "DAROCUR 2959” is also sold by E. Merck. This compound is 4(2- hydroxyethoxy) henyl-(2-hydroxy-2-propyl)ketone.
  • DAROCUR 2959 can also be made copolymerizable through the use of methacrylate ester and maleate halfester compounds. The maleate halfester can be formed .in situ during the copolymerization of the acrylic and vinylic monomers and maleic anhydride in the presence of DAROCUR 2959. The halfester forma ⁇ tion can be "pushed" to completion by the addition of a tertiary amine such as N,N,-dimethylbenzylamine at the termination of the polymerization reaction.
  • the copolymerizable photoinitiator monomer is present in the range of from 0.1% to 10% by weight, and preferably from 0.5% to 5% by weight, in the adhesive copolymer composition.
  • Another monomeric component which may be added to the polymer composition is one or more vinyl esters present in a total amount of 0 up to about 20% by weight based on the total weight of the monomers.
  • Vinyl esters contain from 2 to about 16 carbon atoms in the alkyl group of the acid.
  • Representative of the vinyl esters are vinyl acetate, vinyl butyrate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl versitate, and the like. Vinyl acetate is preferred.
  • the monomer proportions are adjusted in such a way that the adhesive has a glass-transition tempera ⁇ ture of about -30°C or less and at least about 50°C below the use temperature, giving a good balance of adhesion and tack at room temperature and low temper ⁇ atures.
  • the present invention is especially suitable for making hot melt PSAs, which have low melt viscosi ⁇ ties, allowing them to be easily coated out on a web as a thin film, even by a printing process.
  • low melt viscosities are obtained by dilution of the PSA polymer with relatively large quantities of reactive diluents.
  • low melt viscosities are achieved by relatively low initial polymer molecular weight.
  • the PSA polymers of the present invention are compounded with small amounts of multifunctional acrylates or methacrylates, such as diethyleneglycol- diacrylate (DEGDA) , triethyleneglycoldiacrylate (TEGDA) , tripropyleneglycoldiacrylate (TPGDA) , 1,6- hexanedioldiacrylate(HDODA) ,trimethylolpropanetri- acrylate (TMPTA) , trimethylolpropanetrimethacrylate (TMPTMA) , pentaerythritoltriacrylate (PETA) , or the like.
  • the multifunctional acrylates or methacrylates are present in the range of from 0.1% to 10% by weight, preferably from 1% to 5% by weight.
  • the compounded polymer After coating the compounded polymer as a thin film, it can be UV-cured very rapidly with small UV dosages of as low as 3 kJ/m 2 , to produce a PSA of very high cohesive strength and high-temperature shear strength, which retains a good balance of tack and peel performance.
  • the UV radiation in this invention is preferably by conventional, medium-pressure mercury lamps, with emission bands ranging from 240 nm to 410 nm, light intensities from 6 to 10 kWatts/m 2 , and temperatures from 45°C to 125°C at the web surface. Unlike other UV cures, the UV cures of the present invention are performed in an aerobic atmosphere.
  • the PSAs of the present invention respond readily to UV crosslinking, and the coater-ready hot melt PSA composition has an excellent shelf-life as well as an excellent melt pot-life. Storage of the polymer at room temperature of more than about 10 months results in no increase in the viscosity of the polymer. Similarly, exposing the polymer to 100°C for 10 days results in only a slight increase in the viscosity of the polymer, from its initial viscosity of 16 Pascal seconds to only 28 Pascal seconds after 10 days at 100°C.
  • the tack and peel adhesion performance of the PSAs of the present invention are relatively insensitive to wide variations in the UV irradiation dosage needed for cure, to variations in the polymers' initial viscosity, and to levels of added multifunctional acrylic monomers.
  • the decrease in tack and peel adhesion upon accelerated aging is also smaller than in conventional UV-cured PSAs.
  • reaction temperature varies depending on the halflife temperature of the initiators used.
  • the polymerization product is sampled for percent conversion and for melt viscosity measurements.
  • the polymerization product is immediately compounded with the multifunctional acrylic monomer, inside the reactor, before the product is discharged as coater-ready material.
  • Adhesive Coating and UV Cure The compounded polymer is direct-coated on about 50 ⁇ m polyester film at a coating weight ranging from about 30 to about 40 g/m 2 , and is cured by UV radiation from two conventional medium-pressure mercury lamps which have spectral emissions from 240 nm to 410 nm, and light intensities from 6 to 10 kWatts/m 2 .
  • the coated polyester film is carried on a moving web under the UV radiation source, and the web temperature is from about 45°C to about 125°C.
  • the UV dosage which the coated adhesive film receives is controlled by the UV lamp-intensity setting and web speed. All UV cure is performed in an aerobic atmosphere, and no special precautions to exclude air are required.
  • the adhesive film After the adhesive film is cured, it is laminated with a sheet of release liner, for protection, until it is ready for application.
  • solution adhesives or emulsion adhesives are to be coated and cured, the major portion of the low volatiles are removed from the coated material, before UV cure. The volatiles are removed by placing the coated material in a forced-air oven at about 70°C for about 5 minutes before cure, and, to remove the last traces of low volatiles, for another 15 minutes after cure.
  • Samples of the coated adhesive construction are cut in 2.54 cm x about 20 cm test strips.
  • the strips are formed into a loop, which is brought, in an Instron tensile tester, into contact with a standard stainless steel test panel at a rate of about 30 cm/minute, with no other force than the weight of the strip itself. After a brief contact period, the loop is peeled from the test panel at about 30 cm/minute.
  • the force to remove the adhesive loop is measured, in newtons (N)/m. Tests are performed in triplicate.
  • test strips were cut in 2.54 cm x about 20 cm test strips, which were rolled down on standard stainless steel test panels with about a 2 kg rubber-clad steel roller, back and forth once at a rate of about 30 cm/minute. After a dwell time of 20 minutes at standard testing laboratory conditions, the test strips were peeled away from the test panel in an Instron tensile tester at 180° to the test panel, i.e., folded back on itself and parallel to the surface of the panel, at a rate of about 30 cm/minute. The force to remove the adhesive test strip from the test panel was measured in N/m. Tests were performed in triplicate. Possible modes of adhesion failures are the same as above.
  • Static Shear Samples were cut in 1.27 cm x about 5 cm and 2.54 cm x about 6 cm test strips.
  • RTS room temperature
  • the 1.27 cm x 5 cm test strips were applied on a standard stainless steel test panel, making a sample-overlap of 1.27 cm x 1.27 cm with the test panel.
  • the sample portion on the test panel was rolled down with about a 2 kg rubber-clad steel roller, back and forth once at a rate of 30 cm/minute.
  • the free end of the test strip was folded back on itself, and a small hole was made at the free end, where a load of 500 g could be attached during the test.
  • the sample's free end can be reinforced with aluminum foil, cardboard, or the like, to prevent the sample from tearing when the load is applied.
  • the shear test was performed at an elevated temperature (ETS) , either at 70°C, 100°C, or at any higher temperature, the 2.54 cm x 6 cm test strips were used, and were applied on the test panels to make a sample-overlap of 2.54 cm x 2.54 cm with the test panel.
  • ETS elevated temperature
  • the rack with panels, test strips, 500 g load and timing device are placed in an oven, equipped with a constant-temperature-control mechanism.
  • PSA polymer-1 was a control and comprised 58% by weight 2-ethylhexylacrylate, 24% methyl- acrylate, 10% 3-carboxyethylacrylate, and 8% dibutyl- fumarate.
  • P-l had a weight-averaged molecular weight (M-,) of 385,000 and a number-averaged molecular weight (M of 66,000, as determined by size exclusion chromatography (SEC) .
  • SEC size exclusion chromatography
  • P-l had a 100°C Brookfield melt viscosity of 46.5 pascal seconds (Pa.s.), using the #29 spindle at 10 rpm. It was also compounded with 2% by weight of photoinitiator DAROCUR 1173.
  • PSA P-2 was the test material, made according to the present invention, and comprised 2% by weight of the copolymerizable photoinitiator DAROCUR ZLI 3331, 56% 2-ethylhexylacrylate, 24% ethylacrylate, 10% ⁇ - carboxyethylacrylate, and 8% dibutylfumarate.
  • the compositions of the P-l and P-2 are summarized in Table I.
  • FIGs. 1 and 2 illustrate a relatively flat response of looptack and 180° peel adhesion of P-2 to UV radiation dosage.
  • Adhesive performance of PSAs which are made according to the present invention is characterized by a low sensitivity to variations in the starting polymer viscosity, its formulation, and the UV irradiation dosage.
  • Post Cure Coated and UV-cured adhesives of the present invention have better aging stability than adhesives which are made by conventional UV curing methods.
  • Polymer-3 was made according to the present invention.
  • the photoinitiator material used was the alcohol DAROCUR 2959 or 4(2-hydroxyethoxy)phenyl-(2- hydroxy-2-propyl)ketone, which was made copolymerizable through the maleate halfester compound.
  • the maleate halfester was not made in a separate synthesis step, but was made in situ during the polymerization of the monomers which comprise the PSA material.
  • composition of P-3 is summarized in Table VI.
  • the product has a 100°C melt viscosity of 30.4 Pa.s. before compounding. It was subsequently compounded with 4% by weight of HDODA and after coating on 50 ⁇ poly-(ethylene terephthalate) (PET) at a coating weight of 30 g/m 2 and UV-cured.
  • the adhesive performance of the PSA is summarized in Table VII.
  • Coated and UV-cured adhesives of the present invention exhibit good immersion resistance to a number of liquids, provided when the facestock material is not affected by the liquids in the immersion tests.
  • Polymer P-3 was evaluated for an under-the-hood automotive labeling adhesive application, where the labels might be exposed to a number of automotive liquids.
  • 2.54 cm x about 20 cm test samples from the previous illustration were applied to standard stainless steel test panels. After a dwell time of 24 hours, the panels and applied test samples were immersed in the automotive liquids. After the specified times of immersion, the panels and samples were taken out. The adhering liquids were carefully blotted with filter paper, and after a 1-hour recovery at ambient, the test strips were examined for liquid edge penetration and for any changes to the facestocks. Maximum acceptable edge penetration is normally no more than 5 mm. Finally, the test strips were peeled away in a 180° peel angle from the test panels. The results are summarized in
  • Polymer-4 was a scale-up of P-3 from 800 g to
  • PET at a coating weight of 30 g/m 2 was UV-cured.
  • the adhesive performance of P-4 is summarized in Table
  • the present invention have very good pot-lives, even when kept at elevated temperatures.
  • the coater-ready P-4 which contained 4% by weight of HDODA was heated continuously at 100°C in the Thermocell of a Brookfield viscometer, and the
  • melt viscosity followed over several days.
  • the melt viscosity rose from about 16 Pa.s. to only about 22
  • Polymer-5 was made according to the present invention. It contained 2% by weight of the copolymerizable photoinitiator DAROCUR ZLI 3331, and consisted further of 56% 2-ethylhexylacrylate, 24%
  • the scaled-up batch had the following adhesive performance on 50 ⁇ m PET facestock at a coating weight of 30 g/m 2 and after UV cure.
  • the properties of P-5 are summarized in Table XI.
  • the scaled-up, P-5 coater-ready material was stored in closed, 19-liter metal pails, and was retrieved after 10 months of storage under uncontrolled warehouse conditions.
  • the material had an excellent shelf-life.
  • the 100°C melt viscosity rose only to 12.3 Pa.s. after the 10-month storage period.
  • the material was still very UV-reactive; after coating on 50 ⁇ m PET at 30 g/m 2 coating weight and UV cure with only 4 kJ/m 2 , it gave infinite 70°C ETS, without any creep.
  • the formation of high cohesive strength in PSAs by UV cure of the present invention is also 1 applicable to solution-based as well as emulsion- based adhesives.
  • Polymer-6 was made in ethylacetate solution from 52.5% by weight of 2-ethylhexylacrylate, 18% methyl- 5 acrylate, 18% vinylacetate, 8% dioctylmaleate, 3% acrylic acid, and 0.5% DAROCUR ZLI 3331, using Vazo 52 as the polymerization initiator.
  • the composition of P-6 is summarized in Table XII.
  • Polymer-7 was made in emulsion and consisted of 55% by weight of 2-ethylhexylacrylate, 20% methyl- acrylate, 8% dioctylmaleate, 5% acrylic acid, and 1% Of DAROCUR ZLI 3331, using Alipal CO-436 (manufactured by Rhone Poulenc/Triton X-165 (manufactured by Union Carbide) as the surfactant, and t-butylhydroperoxide-FeEDTA as the redox initiator system. The product was compounded with 4% by weight of HDODA based on polymer solids. The composition of P-7 is summarized in Table XIV.
  • UV cure developed high cohesive strength in the adhesive coating, on 50 ⁇ m PET at a coating weight of 30 g/m 2 .
  • the properties of P-7 are summarized in

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Abstract

La présente invention se rapporte à un copolymère pour adhésif autocollant, comprenant: des monomères d'amorçage photochimique copolymérisables tels que des composés de benzoïne, des composés d'acyloïne et des mélanges de ceux-ci; des monomères à faible température de transition vitreuse; et des monomères polyvalents. L'invention se rapporte également à un procédé de préparation de ces copolymères. Le durcissement, par rayonnement actinique, du polymère, est effectué au moyen d'un lumière présentant une longueur d'onde comprise entre 240 et 410 nm environ, à une intensité lumineuse comprise entre 6 et 10 kWatts/m2 environ, et à une température comprise entre 45 °C et 125 °C environ, dans des conditions aérobies. Les adhésifs autocollants obtenus présentent une force d'adhérence et une résistance au cisaillement à haute température qui ne défaillent pas, lors d'un essai par traction de cisaillement statique, après plusieurs milliers de minutes; des caractéristiques d'adhérence comprises entre 300 et 500 N/m environ; des caractéristiques de résistance à l'arrachement comprises entre 550 et 650 N/m environ; une durée de conservation à température ambiante supérieure à 10 mois environ, avec peu ou presque pas d'augmentation dans la viscosité du polymère; ainsi qu'un temps de tenue en fusion d'au moins 10 jours à 100 °C, avec un accroissement minime de la viscosité du polymère.
PCT/US1992/009493 1991-11-05 1992-11-04 Adhesifs autocollants thermofusibles durcissant par rayonnement ultraviolet WO1993009152A1 (fr)

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CA002122921A CA2122921A1 (fr) 1991-11-05 1992-11-04 Adhesifs autocollants thermofusibles, durcissables par les u.v.

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578151A1 (fr) * 1992-07-08 1994-01-12 Beiersdorf Aktiengesellschaft Adhésifs thermofusibles sensibles à la pression pour des produits médicaux
DE4406977A1 (de) * 1994-03-03 1995-09-07 Lohmann Gmbh & Co Kg Verfahren zur Herstellung von Haftklebeschichten, insbesondere von dicken Haftklebeschichten für die Herstellung von selbstklebenden Hochleistungsklebstoffartikeln
WO1997039837A1 (fr) * 1996-04-19 1997-10-30 Minnesota Mining And Manufacturing Company Procede de fabrication d'un enduit
US5741543A (en) * 1995-02-10 1998-04-21 Minnesota Mining And Manufacturing Company Process for the production of an article coated with a crosslinked pressure sensitive adhesive
US5773485A (en) * 1994-07-29 1998-06-30 Minnesota Mining And Manufacturing Company Acrylic syrup curable to a crosslinked viscoelastomeric material
EP1004794A1 (fr) * 1998-11-25 2000-05-31 Xerox Corporation Appareil de jonction à découpes imbriquées utilisant un traitement par ultraviolets
WO2000063314A1 (fr) * 1999-04-14 2000-10-26 Basf Aktiengesellschaft Dispersions reticulables par rayonnement uv pour le contrecollage
WO2003046030A1 (fr) * 2001-11-24 2003-06-05 Tesa Ag Reticulation de polyacrylates initialises par des photo-initiateurs
WO2004081133A1 (fr) * 2003-03-11 2004-09-23 Basf Aktiengesellschaft Adhesif sensible a la pression
US7605212B2 (en) 2004-09-09 2009-10-20 Tesa Se Method for producing contact adhesive masses containing acrylic
WO2010089203A1 (fr) * 2009-02-05 2010-08-12 Tesa Se Ruban adhésif transfert présentant une adhérence différente sur ses deux faces et procédé de fabrication de ce ruban adhésif
US7964249B2 (en) 2000-10-06 2011-06-21 Tesa Se Method for producing crosslinked acrylate hot-melt adhesive compounds
KR101512195B1 (ko) * 2007-11-08 2015-04-15 닛뽕 카바이도 고교 가부시키가이샤 점착제 조성물 및 광학필름
JP2015092003A (ja) * 2015-02-10 2015-05-14 スリーエム イノベイティブ プロパティズ カンパニー アクリル系粘着剤の製造方法
US9546305B2 (en) 2013-03-29 2017-01-17 Ashland Licensing And Intellectual Property Llc Ultraviolet cureable pressure sensitive adhesives comprising bound photoinitiator and vinyl groups

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US3926639A (en) * 1971-11-18 1975-12-16 Sun Chemical Corp Photopolymerizable compositions comprising polycarboxysubstituted benzophenone reaction products
US4144157A (en) * 1974-09-11 1979-03-13 Beiersdorf Aktiengesellschaft Acrylic and methacrylic self-adhesive composition and radiation method of making same
US4737559A (en) * 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
US4914004A (en) * 1986-08-30 1990-04-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Two-layer system
EP0373662A2 (fr) * 1988-12-14 1990-06-20 Sekisui Kagaku Kogyo Kabushiki Kaisha Composition photopolymérisable liquide, produit visco-élastique obtenu à partir de cette composition, et procédé de préparation produit visco-élastique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926639A (en) * 1971-11-18 1975-12-16 Sun Chemical Corp Photopolymerizable compositions comprising polycarboxysubstituted benzophenone reaction products
US4144157A (en) * 1974-09-11 1979-03-13 Beiersdorf Aktiengesellschaft Acrylic and methacrylic self-adhesive composition and radiation method of making same
US4737559A (en) * 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
US4914004A (en) * 1986-08-30 1990-04-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Two-layer system
EP0373662A2 (fr) * 1988-12-14 1990-06-20 Sekisui Kagaku Kogyo Kabushiki Kaisha Composition photopolymérisable liquide, produit visco-élastique obtenu à partir de cette composition, et procédé de préparation produit visco-élastique

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578151A1 (fr) * 1992-07-08 1994-01-12 Beiersdorf Aktiengesellschaft Adhésifs thermofusibles sensibles à la pression pour des produits médicaux
DE4406977A1 (de) * 1994-03-03 1995-09-07 Lohmann Gmbh & Co Kg Verfahren zur Herstellung von Haftklebeschichten, insbesondere von dicken Haftklebeschichten für die Herstellung von selbstklebenden Hochleistungsklebstoffartikeln
US5773485A (en) * 1994-07-29 1998-06-30 Minnesota Mining And Manufacturing Company Acrylic syrup curable to a crosslinked viscoelastomeric material
US5902836A (en) * 1994-07-29 1999-05-11 Minnesota Mining And Manufacturing Company Acrylic syrup curable to a crosslinked viscoelastomeric material
US5741543A (en) * 1995-02-10 1998-04-21 Minnesota Mining And Manufacturing Company Process for the production of an article coated with a crosslinked pressure sensitive adhesive
WO1997039837A1 (fr) * 1996-04-19 1997-10-30 Minnesota Mining And Manufacturing Company Procede de fabrication d'un enduit
US5891530A (en) * 1996-04-19 1999-04-06 Minnesota Mining And Manufacturing Company Method for producing a coating
EP1004794A1 (fr) * 1998-11-25 2000-05-31 Xerox Corporation Appareil de jonction à découpes imbriquées utilisant un traitement par ultraviolets
WO2000063314A1 (fr) * 1999-04-14 2000-10-26 Basf Aktiengesellschaft Dispersions reticulables par rayonnement uv pour le contrecollage
US7964249B2 (en) 2000-10-06 2011-06-21 Tesa Se Method for producing crosslinked acrylate hot-melt adhesive compounds
EP1370590B2 (fr) † 2000-10-06 2012-11-21 Tesa Se Procede de production de composes autoadhesives acrylates reticules
US7271203B2 (en) 2001-11-24 2007-09-18 Tesa Aktiengesellschaft Crosslinking of photoiniator-initialized polyacrylates
US7402632B2 (en) 2001-11-24 2008-07-22 Tesa Aktiengesellschaft 2-Component crosslink of end-functionalized polyacrylates
WO2003046030A1 (fr) * 2001-11-24 2003-06-05 Tesa Ag Reticulation de polyacrylates initialises par des photo-initiateurs
WO2004081133A1 (fr) * 2003-03-11 2004-09-23 Basf Aktiengesellschaft Adhesif sensible a la pression
US7605212B2 (en) 2004-09-09 2009-10-20 Tesa Se Method for producing contact adhesive masses containing acrylic
KR101512195B1 (ko) * 2007-11-08 2015-04-15 닛뽕 카바이도 고교 가부시키가이샤 점착제 조성물 및 광학필름
WO2010089203A1 (fr) * 2009-02-05 2010-08-12 Tesa Se Ruban adhésif transfert présentant une adhérence différente sur ses deux faces et procédé de fabrication de ce ruban adhésif
US9546305B2 (en) 2013-03-29 2017-01-17 Ashland Licensing And Intellectual Property Llc Ultraviolet cureable pressure sensitive adhesives comprising bound photoinitiator and vinyl groups
JP2015092003A (ja) * 2015-02-10 2015-05-14 スリーエム イノベイティブ プロパティズ カンパニー アクリル系粘着剤の製造方法

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CA2122921A1 (fr) 1993-05-13
AU3126993A (en) 1993-06-07

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