CA1157998A - Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-s-triazine - Google Patents
Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-s-triazineInfo
- Publication number
- CA1157998A CA1157998A CA000369335A CA369335A CA1157998A CA 1157998 A CA1157998 A CA 1157998A CA 000369335 A CA000369335 A CA 000369335A CA 369335 A CA369335 A CA 369335A CA 1157998 A CA1157998 A CA 1157998A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- composition
- mixture
- parts
- photoactive
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000000178 monomer Substances 0.000 title claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 31
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 33
- 230000005855 radiation Effects 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 239000006188 syrup Substances 0.000 claims description 14
- 235000020357 syrup Nutrition 0.000 claims description 14
- -1 N-substituted acrylamides Chemical class 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003211 polymerization photoinitiator Substances 0.000 claims 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 241000428199 Mustelinae Species 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical group C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MCNPOZMLKGDJGP-QPJJXVBHSA-N 2-[(e)-2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1\C=C\C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-QPJJXVBHSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OPECTNGATDYLSS-UHFFFAOYSA-N naphthalene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC(S(=O)(=O)Cl)=CC=C21 OPECTNGATDYLSS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000906 photoactive agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F7/0295—Photolytic halogen compounds
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
- C08L2666/36—Nitrogen-containing compounds
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
- Y10S430/121—Nitrogen in heterocyclic ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2809—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including irradiated or wave energy treated component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Abstract
Abstract of the Disclosure The invention concerns a photopolymerizable mixture of (a) acrylic monomer such as 95 parts of an alkyl acrylate and 5 parts of acrylic acid and (b) 0.01 to 2 parts by weight of a chromophore-substituted-halomethyl-s-triazine. The invention differs from the prior art in that the s-triazine has the formula
Description
11S~"18 121,404 C~REG
PHOTOACTIVE MIXTURE OF ACRYLIC MOMOMERS AND
CHROMOP~ORE-SUBSTITUTED HALOMETHYL-S-TRIAZINE
Technical Field This invention concerns photocrosslinkable mixtures of acrylic monomers, especially those which photopolymerize to a pressure-sensitive adhesive state and become crosslinked during the photopolymerization.
Background Art Pressure-sensitive adhesive tape is generally manufactured by coating onto a backing sheet a solution or emulsion of a pressure-sensitive adhesive polymer and heating the coating to drive off the volatile vehicle.
Belgian Patent No. 675l420 published May 16, 1966, concerns a process for making pressure-sensitive adhesive tape which evolves essentially no volatiles. While maintaining an inert atmosphere, a mixture of acrylic monomers and a photoinitiator is coated onto a backing sheet and then polymerized with ultraviolet radiation to a pressure-sensitive adhesive state.
United States Patent No. 4,181,752 (Martens et al.~ discloses a process for makinq pressure-sensitive adhesive tape which, like that of Belgian Patent No.
675,420, involves the photopolymerization of acrylic monomers. While the Belgian patent discloses nothing of the specific intensity and the specific spectral distribution of the irradiation, the Martens patent discloses that these must be controlled in order to attain desirably high cohesive strength and also to attain high peel resistance. It teaches that the polymerizable mixture should be subjected to radiation in the near ultraviolet region at a rate of irradiation in the 300-400 nanometer wavelength range of not more than 7 milliwatts per square centimeter of the mass exposed. Any radiation shorter ~.~
~,
PHOTOACTIVE MIXTURE OF ACRYLIC MOMOMERS AND
CHROMOP~ORE-SUBSTITUTED HALOMETHYL-S-TRIAZINE
Technical Field This invention concerns photocrosslinkable mixtures of acrylic monomers, especially those which photopolymerize to a pressure-sensitive adhesive state and become crosslinked during the photopolymerization.
Background Art Pressure-sensitive adhesive tape is generally manufactured by coating onto a backing sheet a solution or emulsion of a pressure-sensitive adhesive polymer and heating the coating to drive off the volatile vehicle.
Belgian Patent No. 675l420 published May 16, 1966, concerns a process for making pressure-sensitive adhesive tape which evolves essentially no volatiles. While maintaining an inert atmosphere, a mixture of acrylic monomers and a photoinitiator is coated onto a backing sheet and then polymerized with ultraviolet radiation to a pressure-sensitive adhesive state.
United States Patent No. 4,181,752 (Martens et al.~ discloses a process for makinq pressure-sensitive adhesive tape which, like that of Belgian Patent No.
675,420, involves the photopolymerization of acrylic monomers. While the Belgian patent discloses nothing of the specific intensity and the specific spectral distribution of the irradiation, the Martens patent discloses that these must be controlled in order to attain desirably high cohesive strength and also to attain high peel resistance. It teaches that the polymerizable mixture should be subjected to radiation in the near ultraviolet region at a rate of irradiation in the 300-400 nanometer wavelength range of not more than 7 milliwatts per square centimeter of the mass exposed. Any radiation shorter ~.~
~,
- 2 - ~57~'~8 than 300 nanome-ters is lilnited to not rnore than about 10~
of the energy in the 300-~00 nanometers; the same specific intensity and specific spectral distribution of the irradiation are preferred for the practice of the present invention.
Martens teaches that the pressure-sensitive adhesive layer may be crosslinked, particularly where it is desired to irlcrease the cohesive strength of the adhesive without unduly affectin~ its compliance. This can be achieved by utilizing a photoactive crosslinking agent in conjunction with the photoinitiator. Preferred as the photoactive crosslinking agent are certain chromophore-substituted vinylhalomethyl-s-triazines such as 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine which has the formula ~ \ ~ CH=CH ~ OCH3 ''''~
This compound is hereinafter called "MOST".
Disclosure of Invention As does the aforementioned Martens patent, the present invention primarily concerns a photocrosslinkable mixture of acrylic monomers such as alkyl acrylates, especially those which photopolymerize to a pressure-sensitive adhesive state and become crosslinked during the photopolymerization. As in Martens the photocrosslinkable _3_ ~57~98 mixture includes a photoactive agent which is a chromophore- substituted halomethyl-s-triazine, but this differs from MOST in that it has no styryl group. The photoactive s-triazine employed in the present invention can be made by a more simple and hence more economical process than can MOST, has better solubility in acrylic monomer mixtures than does MOST, and tends to provide desirably shortened reaction times and somewhat greater tolerance to oxygen. MOST tends to lend a yellowish color 10 whereas the photoactive s-triazine employed in the invention usually produces no observable color, or in any case much less color than does MOST.
While the present invention primarily concerns (1) photopolymerizable mixtures of acrylic monomers which lS become crosslinked when subjected to ultraviolet radiation, it also concerns (2) photoactive mixtures of acrylic polymers which become crosslinked when subjected to ultraviolet radiation and (3) photoactive mixtures of acrylic monomers which polymerize when exposed to 20 ultraviolet radiation without becoming crosslinked.
Specifically, the present invention concerns a photoactive mixture comprising by weight (a) 100 parts of a composition or a polymer of 50-100 parts of substituted or unsubstituted mono- or multi-functional alkyl acrylate or methacrylate monomers (all of which are hereinafter collectively referred to as "acrylic monomer") and 0-50 parts of copolymerizable monoethylenically unsaturated monomer; and (b) 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein Rl, R2, R3, and R4 are independently ~,S7~38 hydrogen, alkyl (preferably methyl or ethyl) or alkoxy (preferably methoxy or ethoxy) groups, and 1 to 3 of Rl, R2, R3, and R4 are hydrogen.
Preferably the alkyl and alkoxy groups have not more than 12 carbon atoms (see U.S. Patent No. 3,954,475). Alkoxy are preferred over alkyl groups, because they have greater influence on the maximum absorption wavelength. Preferably both R2 and R3 are alkoxy, because this tends to provide shorter reaction times. Adjacent alkoxy substituents may be interconnected to form a ring.
The photoactive _-triazine component (b) may be prepared by the co-trimerization of an aryl nitrile with trichloroacetonitrile in the presence of HCl gas and a Lewis acid such as AlC13, AlBr3, etc.
(Bull. Chem. Soc. Japan, Vol. 42, page 2924 (1969)).
When photopolymerizing acrylic monomer, it may be desir-able to do so stepwise. The preferred first step is to mix acrylic monomer with a photoinitiator which is not a crosslinking agent such that the dissolved amount of the photoinitiator provides up to 0.5~ by weight of the mixture.
The second step is to expose the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoise at ordinary room temperature.
Unless acrylic monomer were first at least partially polymerized, the viscosity of the mixture would be too low to provide uniform coatings of thicknesses most useful for pressure-sensitive adhesive tapes, e.g., 25 to 250 micrometers. The partial photopolymerizing may be stopped at any point simply by turning off the ultraviolet radiation.
,~
~57~38 The third step is to mix with said syrup the above-identified photoactive s-triazine component (b). The modified syrup may be coated onto a backing member and exposed to ultra-violet radiation to complete the - 4a -_5- ~57~'~8 polymerization. Alternatively, the third step may be performed using a syrup which has been prepared by conventional thermal polymerization techniques and has been quenched with air to attain the desired viscosity~
When an uncrosslinked polymer of acrylic monomer is mixed with the photoactive s-triazine component (b) and the mixture is exposed to ultraviolet radiation, the polymer becomes crosslinked if the acrylic monomer comprises an alkyl acrylate. For example, a pressure-sensitive adhesive polymer of an alkyl acrylate which has been polymerized in emulsion or solution may be dissolved in an organic solvent and then mixed with the photoactive s-triazine. After coating this solution onto a flexible backing member and evaporating the solvent, exposure of the coating to ultraviolet radiation causes crosslinking of the polymer. By using an opaque backing member to shield the dried coating from accidental ultraviolet radiation, the uncrosslinked tape may be marketed in commerce and eventually crosslinked by ultimate consumers.
Photoinitiators which are useful for partially polymerizing acrylic monomer without crosslinking include the benzoin ethers (such as benzoin methyl ether or benzoin isopropyl ether)j substituted benzoin ethers (such as anisoin methyl ether), substituted acetophenones (such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenyl-acetophenone), substituted alpha-ketols (such as 2-methyl-2-hydroxypropiophenone), aromatic sulfonyl chlorides (such as 2-naphthalene-sulfonyl chloride) and photoactive oximes ~such as l-phenyl-1,1-propanedione-2-50-ethoxycarbonyl)oxime].
They may be used in amounts which as dissolved provide about 0.001 to 0.5 percent by weight of the alkyl acrylate or methacrylate monomer, preferably at least 0.01 percent.
After adding the above-identified photoactive s-triazine component (b) to acrylic monomer, whether or not partially polymerized to provide a coatable syrup, the -6- ~ S~ ~ ~8 polymeri~ation quickly goes to completion when subjected to ultraviolet radiation. If the acrylic monomer comprises alkyl acrylate, the polymer simultaneously becomes crosslinked. Although the polymerization is exothermic, coatings as thick as 0.5 mm have been quickly polymerized uniformly. To form uniform, bubble-free layers of greater thickness from acrylic monomer, either the amount of the photoactive s-triazine component ~b) should be kept below about 0.5% by weight of the above-identified composition (a) or the intensity of radiation should be reduced so tha~ polymerization proceeds more slowly.
The extent of polymerization can be monitored by measuring the refractive index of the polymerizable mixture. For example, the refractive index may change from about 1.43 for a partially polymerized syrup to about 1.47 at about 100~ reaction. The change in refractive index occurs linearly with conversion of the unsaturated moiety. See, for example, discussions about the method in Polymerization at Advanced Degrees of Conversion, G. P.
Gladyshev and K. M. Gibov, Keter Press, Jerusalem, 1970.
Alkyl acrylates wherein the alkyl group has 4-1 carbon atoms are readily photopolymerized in the practice of the invention to a pressure-sensitive adhesive state, either alone or in combination with various copolymerizable monoethylenically unsaturated monomers, usually at ratios of about 88-99 parts of the alkyl acrylate or acrylates and correspondingly 12-1 parts by weight of the copolymerizable monomer or monomers.
While the present invention is primarily concerned with pressure-sensitive adhesive tapes, the tack-free products can be used as photo-resists as in the aforementioned U.S. Patent No. 3,779,778 or as viscoelastic damping material in such applications as in 35 U. S. Patent No. 3,605,953 (Caldwell et al.) Multifunctional alkyl acrylates such as hexanediol diacrylate and trimethylolpropane triacrylate provide ~57~38 tack-free products. In the absence of alkyl aerylate, alkyl methacrylates also photopolymerize to a taek-free state but without notieeable crosslinking.
In order to enhanee the internal strength of polymerized products of the invention, whether or not they are tack-free, the acrylic monomer should include one or more copolymerizable monoethylenically unsaturated monomers which have highly polar groups such as are present in acrylic acid, methaerylie aeid, itaeonie aeid, acrylamide, methaerylamide, N-substituted aerylamides, acrylonitrile, methacrylonitrile, hydroxyalkyl acrylates, cyanoethyl acrylate, N-vinylpyrrolidone, and maleic anhydride. Other useful copolymerizable monoethylenically unsaturated monomers include alkyl vinyl ethers, vinylidene chloride, styrene, and vinyltoluene.
Other materials whieh can be blended with the photoactive mixture of this invention include tackifiers, reinforcing agents, and other modifiers, some of whieh may copolymerize with the acrylic monomer or photopolymerize independently.
Glass microbubbles having an average diameter of 10 to 200 micrometers can be blended with photoactive mixtures of this invention which polymerize to a pressure-sensitive adhesive state as taught in U.S. Patent No.
25 4,223,067. If the microbubbles comprise 20 to 65 volume percent of the pressure-sensitive adhesive, the polymerized product will have a foam-like appearance and be suitable for uses to which foam-backed pressure-sensitive adhesive tapes are put.
In the eurrent state of the art, photopolymeriza-tion is carried out in an inert atmosphere. Any inert atmosphere such as nitrogen, carbon dioxide, helium or argon is suitable and, as noted above, some oxygen can be tolerated. A sufficiently inert atmosphere can be aehieved by eovering a layer of the photoaetive mixture with a plastic film which is transparent to ultraviolet ,~
'~:i'' ~.~573~8 radiation and irradiating through that film in air.
The peak wavelength of the ultraviolet radiation preferably is close to the wavelength of maximum absorption of the photoactive s-triazine component (b).
S Good results have been attained using a bank of 40-watt fluorescent black lamps. General Electric and Sylvania each market such a lamp designated "F40BL-Black Light".
The GE lamp emits mainly between 310 nm and 430 nm with a maximum at 380 nm. The Sylvania lamp emits mainly between 310 nm and 400 nm with a maximum at 365 nm. Good results have also been obtained with mercury lamps, namely 400 watt and 1000 watt medium-pressure street lights (General Electric HID H400A-33-1). While the fluorescent lamps have been mounted within the chamber which provides an inert atmosphere, the mercury lamps are hotter and were mounted outside the chamber. A sheet of 006-cm heat-resistant glass placed 1.3 cm above the coating to be polymerized served to seal the chamber and to filter out radiation below 310nm.
In using the fluorescent lamps, the operating intensity has usually been adjusted to Z-4 milliwatts/cm2 at a distance of 12.5 cm from the coating. The mercury street lights provided an intensity of about 2 milliwatts/cm2. The intensity of the irradiation was measured with a United Detector Technology 80X Opto-Meter radiometer which had a sandblasted fused silica diffuser, a Kodak 18A filter, and a silicon photodiode. The filter transmi~ted light between 300 and 400 nanometers. The radiometer was calibrated in accordance with the spectral output of each lamp.
Detailed Description Pressure-sensitive adhesive tapes of the examples below employed as the backing member biaxially-oriented polyethylene terephthalate film having a thickness of about 2 mils (50 micrometers). Each tape was slit to a width of 1/2 inch (1.27 cm) and had an ~57~
g adhesive thickness of about 2 mils (50 micrometers).
Tapes of Examples 1-18 were tested for Peel Value and Shear Value as indicated below. All failures in the tests for Shear Value were cohesive.
Peel Value Tape is adhered by its adhesive to a glass plate under the weight of a 4.5-kg hard rubber roller. Peelback at 180 is measured by attaching the free end of the tape to a scale and moving the glass plate away from the scale at a rate of about 3.8 centimeters per second.
Shear Value A strip of tape is adhered by its adhesive to a stainless steel plate under the weight of a 4.5-kg hard rubber roller with a free end of the tape extending beyond the plate and the adhesive contact area being 1/2 inch by 1/2 inch (1.27 cm by 1.27 cm~. After 30 minutes, the plate is placed in an oven at 70C and positioned 2 from the vertical to prevent peeling. After 10 minutes in the oven, a one kg mass is suspended from the free end, and the time at which the mass falls is noted. The test is discontinued if the tape has not failed after 10,000 minutes.
Examples 1 to 11 and Comparative Examples l-C to 7-C
A series of pressure-sensitive adhesive tapes were made by partially photopolymerizing a mixture of, by weight, 90 parts of isooctyl acrylate 10 parts of acrylic acid 0.1 part of 2,2-dimethoxy-2-phenyl acetophenone, which has the structure ~~
~ and which was obtained as "Irgacure" 651.
~57~1~8 The partial photopolymerizing was accomplished in an inert (nitrogen) atmosphere using a bank of 40-watt fluorescent black lights (GE as described above) to provide coatable syrups of a viscosity (Brookfield) of about lS00 cps. A
photoactive s-triazine was added to each syrup, sometimes together with additional "Irgacure" 651, and thoroughly mixed. Each mixture was coated using a conventional knife coater onto biaxially-oriented polyethylene terephthalate film. The coated film was passed through an inert (nitrogen) chamber and irradiated with the same fluorescent lamps to provide pressure-sensitive adhesive layers. The examples employed the photoactive s-triazines of Table I:
TABLE I
Maximum absorption wavelength Extinction Photoactive in CH2C12 coefficient 5 s-triazine M.P. _C (nanometers) x 10-3 ~-N
A ~ ~ CH3 145 147 330 22 C13C yCH3 ~ OCH3 150_151 353 16.5 N
C ~ OCH3 158-160 345 5.2 10 D ~ ~ OCH3 120-123 350 3.2 ii!~57~98 C13C ~CH3 E ~ ~ 90- 91 345 3.9 F ~ ~ 134-135 356 17.8 C13C~
Structures of the photoactive s-triazines in Table I were confirmed by infrared, nuclear magnetic resonance, and mass spectroscopy. Conditions of the chamber atmosphere, the amount of any additional "Irgacure" 651, the exposure, and the Shear Values in minutes are reported in Table II.
All of the tapes had Peel Values of 50-60 ounces per 1/2 inch (110-130 N/100 mm).
~s7~1~8 TABLE II
C~ygen A~ded Example Photoactive s-triazine In Chamber IrgacureZ~Expcsure Shear No. _ Identity W~t. % (~m) ~ (mj) Value (min) l-C M3ST 0.10 100 0.15 36090 5 2-C MDST 0.10 20 0 45010,000
of the energy in the 300-~00 nanometers; the same specific intensity and specific spectral distribution of the irradiation are preferred for the practice of the present invention.
Martens teaches that the pressure-sensitive adhesive layer may be crosslinked, particularly where it is desired to irlcrease the cohesive strength of the adhesive without unduly affectin~ its compliance. This can be achieved by utilizing a photoactive crosslinking agent in conjunction with the photoinitiator. Preferred as the photoactive crosslinking agent are certain chromophore-substituted vinylhalomethyl-s-triazines such as 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine which has the formula ~ \ ~ CH=CH ~ OCH3 ''''~
This compound is hereinafter called "MOST".
Disclosure of Invention As does the aforementioned Martens patent, the present invention primarily concerns a photocrosslinkable mixture of acrylic monomers such as alkyl acrylates, especially those which photopolymerize to a pressure-sensitive adhesive state and become crosslinked during the photopolymerization. As in Martens the photocrosslinkable _3_ ~57~98 mixture includes a photoactive agent which is a chromophore- substituted halomethyl-s-triazine, but this differs from MOST in that it has no styryl group. The photoactive s-triazine employed in the present invention can be made by a more simple and hence more economical process than can MOST, has better solubility in acrylic monomer mixtures than does MOST, and tends to provide desirably shortened reaction times and somewhat greater tolerance to oxygen. MOST tends to lend a yellowish color 10 whereas the photoactive s-triazine employed in the invention usually produces no observable color, or in any case much less color than does MOST.
While the present invention primarily concerns (1) photopolymerizable mixtures of acrylic monomers which lS become crosslinked when subjected to ultraviolet radiation, it also concerns (2) photoactive mixtures of acrylic polymers which become crosslinked when subjected to ultraviolet radiation and (3) photoactive mixtures of acrylic monomers which polymerize when exposed to 20 ultraviolet radiation without becoming crosslinked.
Specifically, the present invention concerns a photoactive mixture comprising by weight (a) 100 parts of a composition or a polymer of 50-100 parts of substituted or unsubstituted mono- or multi-functional alkyl acrylate or methacrylate monomers (all of which are hereinafter collectively referred to as "acrylic monomer") and 0-50 parts of copolymerizable monoethylenically unsaturated monomer; and (b) 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein Rl, R2, R3, and R4 are independently ~,S7~38 hydrogen, alkyl (preferably methyl or ethyl) or alkoxy (preferably methoxy or ethoxy) groups, and 1 to 3 of Rl, R2, R3, and R4 are hydrogen.
Preferably the alkyl and alkoxy groups have not more than 12 carbon atoms (see U.S. Patent No. 3,954,475). Alkoxy are preferred over alkyl groups, because they have greater influence on the maximum absorption wavelength. Preferably both R2 and R3 are alkoxy, because this tends to provide shorter reaction times. Adjacent alkoxy substituents may be interconnected to form a ring.
The photoactive _-triazine component (b) may be prepared by the co-trimerization of an aryl nitrile with trichloroacetonitrile in the presence of HCl gas and a Lewis acid such as AlC13, AlBr3, etc.
(Bull. Chem. Soc. Japan, Vol. 42, page 2924 (1969)).
When photopolymerizing acrylic monomer, it may be desir-able to do so stepwise. The preferred first step is to mix acrylic monomer with a photoinitiator which is not a crosslinking agent such that the dissolved amount of the photoinitiator provides up to 0.5~ by weight of the mixture.
The second step is to expose the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoise at ordinary room temperature.
Unless acrylic monomer were first at least partially polymerized, the viscosity of the mixture would be too low to provide uniform coatings of thicknesses most useful for pressure-sensitive adhesive tapes, e.g., 25 to 250 micrometers. The partial photopolymerizing may be stopped at any point simply by turning off the ultraviolet radiation.
,~
~57~38 The third step is to mix with said syrup the above-identified photoactive s-triazine component (b). The modified syrup may be coated onto a backing member and exposed to ultra-violet radiation to complete the - 4a -_5- ~57~'~8 polymerization. Alternatively, the third step may be performed using a syrup which has been prepared by conventional thermal polymerization techniques and has been quenched with air to attain the desired viscosity~
When an uncrosslinked polymer of acrylic monomer is mixed with the photoactive s-triazine component (b) and the mixture is exposed to ultraviolet radiation, the polymer becomes crosslinked if the acrylic monomer comprises an alkyl acrylate. For example, a pressure-sensitive adhesive polymer of an alkyl acrylate which has been polymerized in emulsion or solution may be dissolved in an organic solvent and then mixed with the photoactive s-triazine. After coating this solution onto a flexible backing member and evaporating the solvent, exposure of the coating to ultraviolet radiation causes crosslinking of the polymer. By using an opaque backing member to shield the dried coating from accidental ultraviolet radiation, the uncrosslinked tape may be marketed in commerce and eventually crosslinked by ultimate consumers.
Photoinitiators which are useful for partially polymerizing acrylic monomer without crosslinking include the benzoin ethers (such as benzoin methyl ether or benzoin isopropyl ether)j substituted benzoin ethers (such as anisoin methyl ether), substituted acetophenones (such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenyl-acetophenone), substituted alpha-ketols (such as 2-methyl-2-hydroxypropiophenone), aromatic sulfonyl chlorides (such as 2-naphthalene-sulfonyl chloride) and photoactive oximes ~such as l-phenyl-1,1-propanedione-2-50-ethoxycarbonyl)oxime].
They may be used in amounts which as dissolved provide about 0.001 to 0.5 percent by weight of the alkyl acrylate or methacrylate monomer, preferably at least 0.01 percent.
After adding the above-identified photoactive s-triazine component (b) to acrylic monomer, whether or not partially polymerized to provide a coatable syrup, the -6- ~ S~ ~ ~8 polymeri~ation quickly goes to completion when subjected to ultraviolet radiation. If the acrylic monomer comprises alkyl acrylate, the polymer simultaneously becomes crosslinked. Although the polymerization is exothermic, coatings as thick as 0.5 mm have been quickly polymerized uniformly. To form uniform, bubble-free layers of greater thickness from acrylic monomer, either the amount of the photoactive s-triazine component ~b) should be kept below about 0.5% by weight of the above-identified composition (a) or the intensity of radiation should be reduced so tha~ polymerization proceeds more slowly.
The extent of polymerization can be monitored by measuring the refractive index of the polymerizable mixture. For example, the refractive index may change from about 1.43 for a partially polymerized syrup to about 1.47 at about 100~ reaction. The change in refractive index occurs linearly with conversion of the unsaturated moiety. See, for example, discussions about the method in Polymerization at Advanced Degrees of Conversion, G. P.
Gladyshev and K. M. Gibov, Keter Press, Jerusalem, 1970.
Alkyl acrylates wherein the alkyl group has 4-1 carbon atoms are readily photopolymerized in the practice of the invention to a pressure-sensitive adhesive state, either alone or in combination with various copolymerizable monoethylenically unsaturated monomers, usually at ratios of about 88-99 parts of the alkyl acrylate or acrylates and correspondingly 12-1 parts by weight of the copolymerizable monomer or monomers.
While the present invention is primarily concerned with pressure-sensitive adhesive tapes, the tack-free products can be used as photo-resists as in the aforementioned U.S. Patent No. 3,779,778 or as viscoelastic damping material in such applications as in 35 U. S. Patent No. 3,605,953 (Caldwell et al.) Multifunctional alkyl acrylates such as hexanediol diacrylate and trimethylolpropane triacrylate provide ~57~38 tack-free products. In the absence of alkyl aerylate, alkyl methacrylates also photopolymerize to a taek-free state but without notieeable crosslinking.
In order to enhanee the internal strength of polymerized products of the invention, whether or not they are tack-free, the acrylic monomer should include one or more copolymerizable monoethylenically unsaturated monomers which have highly polar groups such as are present in acrylic acid, methaerylie aeid, itaeonie aeid, acrylamide, methaerylamide, N-substituted aerylamides, acrylonitrile, methacrylonitrile, hydroxyalkyl acrylates, cyanoethyl acrylate, N-vinylpyrrolidone, and maleic anhydride. Other useful copolymerizable monoethylenically unsaturated monomers include alkyl vinyl ethers, vinylidene chloride, styrene, and vinyltoluene.
Other materials whieh can be blended with the photoactive mixture of this invention include tackifiers, reinforcing agents, and other modifiers, some of whieh may copolymerize with the acrylic monomer or photopolymerize independently.
Glass microbubbles having an average diameter of 10 to 200 micrometers can be blended with photoactive mixtures of this invention which polymerize to a pressure-sensitive adhesive state as taught in U.S. Patent No.
25 4,223,067. If the microbubbles comprise 20 to 65 volume percent of the pressure-sensitive adhesive, the polymerized product will have a foam-like appearance and be suitable for uses to which foam-backed pressure-sensitive adhesive tapes are put.
In the eurrent state of the art, photopolymeriza-tion is carried out in an inert atmosphere. Any inert atmosphere such as nitrogen, carbon dioxide, helium or argon is suitable and, as noted above, some oxygen can be tolerated. A sufficiently inert atmosphere can be aehieved by eovering a layer of the photoaetive mixture with a plastic film which is transparent to ultraviolet ,~
'~:i'' ~.~573~8 radiation and irradiating through that film in air.
The peak wavelength of the ultraviolet radiation preferably is close to the wavelength of maximum absorption of the photoactive s-triazine component (b).
S Good results have been attained using a bank of 40-watt fluorescent black lamps. General Electric and Sylvania each market such a lamp designated "F40BL-Black Light".
The GE lamp emits mainly between 310 nm and 430 nm with a maximum at 380 nm. The Sylvania lamp emits mainly between 310 nm and 400 nm with a maximum at 365 nm. Good results have also been obtained with mercury lamps, namely 400 watt and 1000 watt medium-pressure street lights (General Electric HID H400A-33-1). While the fluorescent lamps have been mounted within the chamber which provides an inert atmosphere, the mercury lamps are hotter and were mounted outside the chamber. A sheet of 006-cm heat-resistant glass placed 1.3 cm above the coating to be polymerized served to seal the chamber and to filter out radiation below 310nm.
In using the fluorescent lamps, the operating intensity has usually been adjusted to Z-4 milliwatts/cm2 at a distance of 12.5 cm from the coating. The mercury street lights provided an intensity of about 2 milliwatts/cm2. The intensity of the irradiation was measured with a United Detector Technology 80X Opto-Meter radiometer which had a sandblasted fused silica diffuser, a Kodak 18A filter, and a silicon photodiode. The filter transmi~ted light between 300 and 400 nanometers. The radiometer was calibrated in accordance with the spectral output of each lamp.
Detailed Description Pressure-sensitive adhesive tapes of the examples below employed as the backing member biaxially-oriented polyethylene terephthalate film having a thickness of about 2 mils (50 micrometers). Each tape was slit to a width of 1/2 inch (1.27 cm) and had an ~57~
g adhesive thickness of about 2 mils (50 micrometers).
Tapes of Examples 1-18 were tested for Peel Value and Shear Value as indicated below. All failures in the tests for Shear Value were cohesive.
Peel Value Tape is adhered by its adhesive to a glass plate under the weight of a 4.5-kg hard rubber roller. Peelback at 180 is measured by attaching the free end of the tape to a scale and moving the glass plate away from the scale at a rate of about 3.8 centimeters per second.
Shear Value A strip of tape is adhered by its adhesive to a stainless steel plate under the weight of a 4.5-kg hard rubber roller with a free end of the tape extending beyond the plate and the adhesive contact area being 1/2 inch by 1/2 inch (1.27 cm by 1.27 cm~. After 30 minutes, the plate is placed in an oven at 70C and positioned 2 from the vertical to prevent peeling. After 10 minutes in the oven, a one kg mass is suspended from the free end, and the time at which the mass falls is noted. The test is discontinued if the tape has not failed after 10,000 minutes.
Examples 1 to 11 and Comparative Examples l-C to 7-C
A series of pressure-sensitive adhesive tapes were made by partially photopolymerizing a mixture of, by weight, 90 parts of isooctyl acrylate 10 parts of acrylic acid 0.1 part of 2,2-dimethoxy-2-phenyl acetophenone, which has the structure ~~
~ and which was obtained as "Irgacure" 651.
~57~1~8 The partial photopolymerizing was accomplished in an inert (nitrogen) atmosphere using a bank of 40-watt fluorescent black lights (GE as described above) to provide coatable syrups of a viscosity (Brookfield) of about lS00 cps. A
photoactive s-triazine was added to each syrup, sometimes together with additional "Irgacure" 651, and thoroughly mixed. Each mixture was coated using a conventional knife coater onto biaxially-oriented polyethylene terephthalate film. The coated film was passed through an inert (nitrogen) chamber and irradiated with the same fluorescent lamps to provide pressure-sensitive adhesive layers. The examples employed the photoactive s-triazines of Table I:
TABLE I
Maximum absorption wavelength Extinction Photoactive in CH2C12 coefficient 5 s-triazine M.P. _C (nanometers) x 10-3 ~-N
A ~ ~ CH3 145 147 330 22 C13C yCH3 ~ OCH3 150_151 353 16.5 N
C ~ OCH3 158-160 345 5.2 10 D ~ ~ OCH3 120-123 350 3.2 ii!~57~98 C13C ~CH3 E ~ ~ 90- 91 345 3.9 F ~ ~ 134-135 356 17.8 C13C~
Structures of the photoactive s-triazines in Table I were confirmed by infrared, nuclear magnetic resonance, and mass spectroscopy. Conditions of the chamber atmosphere, the amount of any additional "Irgacure" 651, the exposure, and the Shear Values in minutes are reported in Table II.
All of the tapes had Peel Values of 50-60 ounces per 1/2 inch (110-130 N/100 mm).
~s7~1~8 TABLE II
C~ygen A~ded Example Photoactive s-triazine In Chamber IrgacureZ~Expcsure Shear No. _ Identity W~t. % (~m) ~ (mj) Value (min) l-C M3ST 0.10 100 0.15 36090 5 2-C MDST 0.10 20 0 45010,000
3-C MOST 0.20 20 0.25 45010,000
4-C MDST O .10 20 0.25 4501,100
5-C M~ST 0.10 300 0 450225
6-C MDST 0.10 300 0.25 4502,800 107-C MDST 0.20 300 0 45010,000 1 A 0.05 300 0 45010,000 2 A 0.10 100 0 150900 3 A 0.15 100 0 15010,000 4 A 0.10 100 0 22510,000 15 5 B 0.10 100 0 16610,000 6 B 0.15 100 0 150101
7 B 0.2 100 0 12510,000
8 C 0.2 30 0 14010,000
9 D 0.2 30 0.1 20010,000 2010 E 0.2 30 0.1 30010,000 11 F 0.2 30 0.1 20010,000 ~'~57~'~8 Exa~ s 12 to 14 _ A series of pressure-sensitive adhesive tapes were prepared and irradiated as in Example 1 to 11 except using different acrylic monomers and various photoactive s-triazines as indicated in Table III, except that each photopolymerizable mixture of Examples 12 to 14 employed 0.15 part of Photoactive s-triazine B, Comparative Examples 12-C to 14-C included no photoactive s-triazine, and Example 14 and Comparative Example 14-C included 0.2 part of 2,2-dimethoxy-2-phenylacetophenone.
TABLE III
Shear 5 Example Acrylic PhotoactiveValue No. Monomers s-triazine(min) 12 isooctylacrylate:
acrylic acid:
2-cyanoethyl acrylate (74:10:16) B 10,000 12-C isooctylacrylate:
acrylic acid:
2-cyanoethyl acrylate (74:10:16) None 30 15 13 isooctylacrylate:
acrylic acid (94:6) B 10,000*
13-C isooctylacrylate:
acrylic acid (94:6) None 8*
-15~ ~ 579~
14 isooctylacrylate:
N(n-butyl)acrylamide (66:34) B 2,400**
14-C isooctylacrylate:
N(n-butyl)acrylamide (66:34) None 42**
. _ _ _ _ * adhesive contact area 1/2 by 1 inch (1.27 by 2.54 cm) ** adhesive contact area 1/2 by 1 inch (1.27 by 2.54 cm) and tested at room temperature -A pressure-sensitive adhesive tape was prepared from a 50% solution in heptane/toluene/methanol 56/24/20 of a 95:5 polymer of 2-ethylhexyl acrylate:acrylamide which had been solution-polymerized to substantially 100% conversion. Photoactive s-triazine B
was added to the solution (0.165% of dry weight adhesive) and thoroughly mixed. This was knife-coated [4-mil (0.1 mm) orifice] onto a backing member, dried at 135C for 5 minutes, and then irradiated in air using a standard medium-pressure mercury lamp (300 watts/inch) at 30 m/min.
20 (350 mj/cm2). The irradiated tape (Example 15) and an otherwise identical unirradiated tape (Comparative Example 15-C) had Shear Values [except measured at room temperature and a contact area of 1/2 by 1 inch (1.27 cm by 2.54 cm)] of 10,000 and 100 minutes, respectively.
A pressure-sensitive adhesive tape was prepared as in Example 15, except that a 94:6 polymer of 2-ethylhexyl acrylate:acrylamide was used and Photoactive ~57~
s-triazine A was used instead of Photoactive s-triazine B
and in an amount of 0.2~ of dry weight adhesive, and the solvent was removed by vacuum and heat at a temperature less than 160C. The dried adhesive was hot-melt coated to 2 thickness of 2 mils (0.05 mm) and then irradiated in air using the same lamp as in Example 15 at half the web speed (700 mj/cm2). The irradiated tape (Example 16) and an unir-radiated tape (Comparative Example 16-C) had Shear Values (measured as in Example 15) of 10,000 and 400 minutes, respectively.
A polymer of isooctyl acrylate and acrylic acid (95.5:4.5) was prepared by a conventional emulsion-polymerization technique. The polymer was dried and redissolved in 70:30 heptane:isopropanol, 25% solids. To 100 parts of the solution was added 0.05 part of Photoactive s-triazine B, and this was thoroughly mixed.
The mixture was knife-coated [10-mil (0.25 mm) orifice]
onto a backing member and dried at 70C for 5 minutes.
The resulting pressure-sensitive adhesive layer was exposed in the presence of air to ultraviolet irradiation as described in Examples 1-11. The irradiated tape (Example 17) and an otherwise identical unirradiated tape (Comparative Example 17-C) were tested for Peel Value and Shear Value [except 1/2 by 1 inch (1.25 by 2.54 cm) contact area] with results indicated below:
Peel Value Shear Value Tape of (N/100 mm ) (minutes) Example 17 37 10,000 Compa~ative Example 17-C 37 2 Tapes were prepared from a commercial pressure-sensitive adhesive which is understood to be a copolymer ~57~98 comprising a major proportion of 2-ethylhexyl acrylate and minor proportions of vinyl a ~tate, ethyl acrylate and acrylic acid (Ashland "Aroset 1044-Z-40)o This was obtained as a 40% solution, diluted with toluene to 20%
solids, and Photoactive s-triazine B (0~15% of dry weight adhesive) was added. After thorough mixing, the solution was knife coated (0.4-mm orifice) onto a backing member and dried at 70C for 15 minutes. The resultant tape (Example 18) was irradiated as in Examples 1-11) in
TABLE III
Shear 5 Example Acrylic PhotoactiveValue No. Monomers s-triazine(min) 12 isooctylacrylate:
acrylic acid:
2-cyanoethyl acrylate (74:10:16) B 10,000 12-C isooctylacrylate:
acrylic acid:
2-cyanoethyl acrylate (74:10:16) None 30 15 13 isooctylacrylate:
acrylic acid (94:6) B 10,000*
13-C isooctylacrylate:
acrylic acid (94:6) None 8*
-15~ ~ 579~
14 isooctylacrylate:
N(n-butyl)acrylamide (66:34) B 2,400**
14-C isooctylacrylate:
N(n-butyl)acrylamide (66:34) None 42**
. _ _ _ _ * adhesive contact area 1/2 by 1 inch (1.27 by 2.54 cm) ** adhesive contact area 1/2 by 1 inch (1.27 by 2.54 cm) and tested at room temperature -A pressure-sensitive adhesive tape was prepared from a 50% solution in heptane/toluene/methanol 56/24/20 of a 95:5 polymer of 2-ethylhexyl acrylate:acrylamide which had been solution-polymerized to substantially 100% conversion. Photoactive s-triazine B
was added to the solution (0.165% of dry weight adhesive) and thoroughly mixed. This was knife-coated [4-mil (0.1 mm) orifice] onto a backing member, dried at 135C for 5 minutes, and then irradiated in air using a standard medium-pressure mercury lamp (300 watts/inch) at 30 m/min.
20 (350 mj/cm2). The irradiated tape (Example 15) and an otherwise identical unirradiated tape (Comparative Example 15-C) had Shear Values [except measured at room temperature and a contact area of 1/2 by 1 inch (1.27 cm by 2.54 cm)] of 10,000 and 100 minutes, respectively.
A pressure-sensitive adhesive tape was prepared as in Example 15, except that a 94:6 polymer of 2-ethylhexyl acrylate:acrylamide was used and Photoactive ~57~
s-triazine A was used instead of Photoactive s-triazine B
and in an amount of 0.2~ of dry weight adhesive, and the solvent was removed by vacuum and heat at a temperature less than 160C. The dried adhesive was hot-melt coated to 2 thickness of 2 mils (0.05 mm) and then irradiated in air using the same lamp as in Example 15 at half the web speed (700 mj/cm2). The irradiated tape (Example 16) and an unir-radiated tape (Comparative Example 16-C) had Shear Values (measured as in Example 15) of 10,000 and 400 minutes, respectively.
A polymer of isooctyl acrylate and acrylic acid (95.5:4.5) was prepared by a conventional emulsion-polymerization technique. The polymer was dried and redissolved in 70:30 heptane:isopropanol, 25% solids. To 100 parts of the solution was added 0.05 part of Photoactive s-triazine B, and this was thoroughly mixed.
The mixture was knife-coated [10-mil (0.25 mm) orifice]
onto a backing member and dried at 70C for 5 minutes.
The resulting pressure-sensitive adhesive layer was exposed in the presence of air to ultraviolet irradiation as described in Examples 1-11. The irradiated tape (Example 17) and an otherwise identical unirradiated tape (Comparative Example 17-C) were tested for Peel Value and Shear Value [except 1/2 by 1 inch (1.25 by 2.54 cm) contact area] with results indicated below:
Peel Value Shear Value Tape of (N/100 mm ) (minutes) Example 17 37 10,000 Compa~ative Example 17-C 37 2 Tapes were prepared from a commercial pressure-sensitive adhesive which is understood to be a copolymer ~57~98 comprising a major proportion of 2-ethylhexyl acrylate and minor proportions of vinyl a ~tate, ethyl acrylate and acrylic acid (Ashland "Aroset 1044-Z-40)o This was obtained as a 40% solution, diluted with toluene to 20%
solids, and Photoactive s-triazine B (0~15% of dry weight adhesive) was added. After thorough mixing, the solution was knife coated (0.4-mm orifice) onto a backing member and dried at 70C for 15 minutes. The resultant tape (Example 18) was irradiated as in Examples 1-11) in
10 comparison to an unirradiated tape (Examples 18-C) which was identical except that it did not have any photoactive component. Test results were Shear Value Tape of (minutes) Example 18 4380 Comparative Example 18-C 365 In each o the pressure-sensitive adhesive tapes of Examples 1 to 18, the adhesive layer was permanently bonded to the polyethylene terephthalate backing member.
For many potential uses o the invention, the adhesiv~
20 layer would be formed on a backing member having a low-adhesion layer from which the adhesive layer could be transferred.
EXAMPLES 19 TO 22 AND COMPARATIVE EXAMPLES l9-C TO 22-C
To investigate further the crosslinking ability of the photoacti~e s-triazines, polymers were prepared by 25 mixing "Irgacure' 651 (identified in Examples 1-11) or a photoactive s-triazine with various acrylic monomers.
Each mixture was purged with nitrogen and irradiated with a bank of 40-watt fluorescent black lights (GE as described above) until substantially complete conversion 30 of the unsaturated moietyO Solubility of the resulting polymers was tested in ethyl acetate after shaking at room temperature for 24 hours, except that Example 20 and ~1~79~8 Comparative Example 20-C were tested in ethyl acetate/methanol (90/10). Results are shown in Table IV.
TABLE IV
Example Acrylic Photoactive s-triazine Irgacure~
No. monomers (Identity) (W~t%) (W~t %) Solubility . _ 19 isooctyl acrylate B 0.15 0 gel l9-C 0 0.2 soluble isooctyl acrylate: F 0.15 0 gel 20-C acrylic acid 0 0.2 soluble (70:30) 10 21 isooctyl acrylate: B 0.15 0 gel 21-C n-octyl methacrylate 0 0.2 soluble (80:20) 22 n-butyl acrylate B 0.15 0 gel 22-C 0 0.2 soluble 15 As compared to Photoactive s-triazine A, surprisingly beneficial results have been achieved when using a chromophore-substituted halomethyl-s-triazine of the formula < c ~ 3 wherein R2 and R3 are alkoxy and at least one of Rl and R4 is hydrogen and the other is alkoxy or hydrogen.
Experiments tend to indicate that such s-triazines provide significantly shortened reaction times as compared to Photo-active s-triazine A. This may be in part due to better matching of the maximum absorption 7~'~S
wavelength of the s-triazine to the peak wavelengths of commercially available ultraviolet lamps while retaining desirably high extinction coefficients.
The R2 and R3 substituents may be interconnected to form a ring, specifically Cl3C -(ÇH2)n ~?~-1 Cl C' wherein n is l, 2 or 3. This improves solubility in acrylic monomer. The solubilities of Photoactive-s-triazines A and F are about equal and appreciably better than that of Photoactive-s-triazine B.
For many potential uses o the invention, the adhesiv~
20 layer would be formed on a backing member having a low-adhesion layer from which the adhesive layer could be transferred.
EXAMPLES 19 TO 22 AND COMPARATIVE EXAMPLES l9-C TO 22-C
To investigate further the crosslinking ability of the photoacti~e s-triazines, polymers were prepared by 25 mixing "Irgacure' 651 (identified in Examples 1-11) or a photoactive s-triazine with various acrylic monomers.
Each mixture was purged with nitrogen and irradiated with a bank of 40-watt fluorescent black lights (GE as described above) until substantially complete conversion 30 of the unsaturated moietyO Solubility of the resulting polymers was tested in ethyl acetate after shaking at room temperature for 24 hours, except that Example 20 and ~1~79~8 Comparative Example 20-C were tested in ethyl acetate/methanol (90/10). Results are shown in Table IV.
TABLE IV
Example Acrylic Photoactive s-triazine Irgacure~
No. monomers (Identity) (W~t%) (W~t %) Solubility . _ 19 isooctyl acrylate B 0.15 0 gel l9-C 0 0.2 soluble isooctyl acrylate: F 0.15 0 gel 20-C acrylic acid 0 0.2 soluble (70:30) 10 21 isooctyl acrylate: B 0.15 0 gel 21-C n-octyl methacrylate 0 0.2 soluble (80:20) 22 n-butyl acrylate B 0.15 0 gel 22-C 0 0.2 soluble 15 As compared to Photoactive s-triazine A, surprisingly beneficial results have been achieved when using a chromophore-substituted halomethyl-s-triazine of the formula < c ~ 3 wherein R2 and R3 are alkoxy and at least one of Rl and R4 is hydrogen and the other is alkoxy or hydrogen.
Experiments tend to indicate that such s-triazines provide significantly shortened reaction times as compared to Photo-active s-triazine A. This may be in part due to better matching of the maximum absorption 7~'~S
wavelength of the s-triazine to the peak wavelengths of commercially available ultraviolet lamps while retaining desirably high extinction coefficients.
The R2 and R3 substituents may be interconnected to form a ring, specifically Cl3C -(ÇH2)n ~?~-1 Cl C' wherein n is l, 2 or 3. This improves solubility in acrylic monomer. The solubilities of Photoactive-s-triazines A and F are about equal and appreciably better than that of Photoactive-s-triazine B.
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A photoactive mixture comprising by weight (a) 100 parts of a composition or a polymer of 50-100 parts of acrylic monomer and 0-50 parts of copolymerizable mono-ethylenically unsaturated monomer and (b) 0.01 to 2 parts of a chromophore-substituted halo-methyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alkyl, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 are hydrogen.
2. A photoactive mixture as defined in claim 1 wherein said alkyl or alkoxy groups have at most 12 carbon atoms.
3. A photoactive mixture as defined in claim 2 wherein at least two of said groups are alkoxy.
4. A photoactive mixture as defined in claim 3 wherein two adjacent alkoxy groups are interconnected to form a ring.
5. A photoactive mixture as defined in claims 1 or 2 wherein said composition or polymer (a) is a composition which is partially polymerized and has a coatable viscosity of 300 to 20,000 centipoises at ordinary room temperature.
6. A photoactive mixture as defined in claims 1 or 2 wherein said composition or polymer (a) is a polymer of an alkyl acrylate.
7. A solution of a photoactive mixture as defined in claim 1 or 2 wherein said composition or polymer (a) is a polymer of an alkyl acrylate in organic solvent.
8. A photoactive mixture as defined in claim 1 wherein the s-triazine (b) is wherein n is 1, 2 or 3.
9. A photoactive mixture as defined in claim 1 wherein the composition or polymer (a) comprises a compo-sition or parially polymerized composition of (1) 88-99 parts of alkyl acrylate having 4-12 carbon atoms in its alkyl groups or alkyl acrylates having an average of 4-12 carbon atoms in their alkyl groups and (2) correspondingly 12-1 parts of said copolymerizable monomer and is polymerizable to a pressure-sensitive adhesive state.
10. A photoactive mixture as defined in claims 1 or 9 wherein at least part of said copolymerizable monomer has highly polar groups.
11. A photoactive mixture as defined in claims 1 or 9 wherein at least part of the copolymerizable monomer has highly polar groups which are at least one of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacryl-amide, acrylonitrile, methacrylonitrile, N-substituted acrylamides, hydroxyalkyl acrylates, cyanoethyl acrylate, N-vinylpyrrolidone, and maleic anhydride.
12. The product of photopolymerizing the photo-active mixture of claim 1 or 2 to about 100% conversion of the unsaturated moiety, said composition or polymer (a) having been partially polymerized and having a coatable viscosity of 300 to 20,000 centipoises at ordinary room temperature.
13. A tape comprising a flexible backing member and a coating of a photoactive mixture as defined in claim 1 or 2 wherein said composition or polymer (a) is a polymer of an alkyl acrylate.
14. A roll of tape as defined in claim 1 or 2 wherein said coating or polymer (a) is a polymer of an alkyl acrylate and the flexible backing member is opaque in order to shield said photoactive mixture from accidental ultraviolet radiation.
15. Pressure-sensitive adhesive tape comprising a backing member and a pressure-sensitive adhesive coating obtained by photopolymerizing a composition or partially polymerized composition as defined in claim 9.
16. Method comprising the steps of (1) mixing by weight (a) 100 parts of a composition or a polymer of 50-100 parts of acrylic monomer and 0-50 parts of copolymerizable monoethylenically unsaturated monomer and (b) 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alkyl, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 are hydrogen, (2) applying the mixture to a substrate, (3) exposing the applied mixture to ultraviolet radiation.
17. Method as defined in claim 16 wherein said composition or polymer (a) consists essentially of a partially polymerized composition having a coatable viscosity of 300 to 20,000 centipoises at ordinary room temperature, step (2) involves coating said mixture onto a flexible backing member, and in step (3) the coated mixture is photopolymerized.
18. Method as defined in claim 16 wherein said composition or polymer (a) is a polymer of an alkyl acrylate, step (2) involves coating onto a flexible backing member a solution of said polymer in an organic solvent, there is an additional step between steps (2) and (3) involving driving off the solvent, and in step (3) the polymer becomes crosslinked.
19. Method as defined in either of claim 17 or claim 18 wherein said composition or polymer (a) is selected such that the applied mixture after being exposed to ultraviolet radiation in step (3) is in a pressure-sensitive adhesive state.
20. Method of making a polymer in accordance with the method of claim 16 comprising the steps of:
(1) mixing by weight (a) 100 parts of an unpolymerized composition of 50-100 parts of acrylic monomer and 0-50 parts of copolymerizable monoethylenically unsaturated monomer and (b) an addition-polymerization photoinitiator which is activatable by ultraviolet radiation, is not a crosslinking agent, and is dissolved in an amount providing 0.001 to 0.5 percent of the composition (a), (2) exposing the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoises at ordinary room temperature, (3) mixing with said syrup 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alkyl, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 are hydrogen, (4) coating said syrup onto a backing member to provide a layer having a thickness of about 25-250 micrometers, and (5) in an inert atmosphere, irradiating the coating with ultraviolet radiation to further polymerize it to a substantially completely polymerized, crosslinked state.
(1) mixing by weight (a) 100 parts of an unpolymerized composition of 50-100 parts of acrylic monomer and 0-50 parts of copolymerizable monoethylenically unsaturated monomer and (b) an addition-polymerization photoinitiator which is activatable by ultraviolet radiation, is not a crosslinking agent, and is dissolved in an amount providing 0.001 to 0.5 percent of the composition (a), (2) exposing the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoises at ordinary room temperature, (3) mixing with said syrup 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alkyl, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 are hydrogen, (4) coating said syrup onto a backing member to provide a layer having a thickness of about 25-250 micrometers, and (5) in an inert atmosphere, irradiating the coating with ultraviolet radiation to further polymerize it to a substantially completely polymerized, crosslinked state.
21. Method of making a flexible pressure-sensitive adhesive tape in accordance with the method of claim 16 comprising the steps of:
(1) mixing by weight (a) an unpolymerized composition of (i) 88-99 part of alkyl acrylate having 4-12 carbon atoms in its alkyl group or alkyl acrylates having an average of 4-12 carbon atoms in their alkyl groups and (ii) correspondingly 1-12 parts of a copolymerizable monomer, which composition is polymerizable to a pressure-sensitive state and (b) an addition-polymerization photoinitiator which is activatable by ultraviolet radiation, is not a crosslinking agent, and is dissolved in an amount providing 0.001 to 0.5 percent of the composition (a), (2) exposing the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoises at ordinary room temperature, (3) mixing with said syrup 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alky, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 is hydrogen, (4) coating said modified syrup onto a flexible backing member to provide a layer having a thickness of about 25-250 micrometers, and (5) in an inert atmosphere, irradiating the coating with ultraviolet radiation to further polymerize it to a pressure-sensitive adhesive state.
(1) mixing by weight (a) an unpolymerized composition of (i) 88-99 part of alkyl acrylate having 4-12 carbon atoms in its alkyl group or alkyl acrylates having an average of 4-12 carbon atoms in their alkyl groups and (ii) correspondingly 1-12 parts of a copolymerizable monomer, which composition is polymerizable to a pressure-sensitive state and (b) an addition-polymerization photoinitiator which is activatable by ultraviolet radiation, is not a crosslinking agent, and is dissolved in an amount providing 0.001 to 0.5 percent of the composition (a), (2) exposing the mixture to ultraviolet radiation to provide a partially-polymerized syrup having a viscosity of 300 to 20,000 centipoises at ordinary room temperature, (3) mixing with said syrup 0.01 to 2 parts of a chromophore-substituted halomethyl-s-triazine of the formula wherein R1, R2, R3, and R4 are independently hydrogen, alky, or alkoxy groups, and 1 to 3 of R1, R2, R3, and R4 is hydrogen, (4) coating said modified syrup onto a flexible backing member to provide a layer having a thickness of about 25-250 micrometers, and (5) in an inert atmosphere, irradiating the coating with ultraviolet radiation to further polymerize it to a pressure-sensitive adhesive state.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/121,404 US4330590A (en) | 1980-02-14 | 1980-02-14 | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine |
US121,404 | 1987-11-16 |
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Publication Number | Publication Date |
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CA1157998A true CA1157998A (en) | 1983-11-29 |
Family
ID=22396494
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Application Number | Title | Priority Date | Filing Date |
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CA000369335A Expired CA1157998A (en) | 1980-02-14 | 1981-01-26 | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-s-triazine |
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US (1) | US4330590A (en) |
EP (1) | EP0045802B1 (en) |
JP (1) | JPH0372664B2 (en) |
KR (1) | KR840001929B1 (en) |
BR (1) | BR8106438A (en) |
CA (1) | CA1157998A (en) |
DE (1) | DE3105343A1 (en) |
ES (1) | ES499310A0 (en) |
IT (1) | IT1142313B (en) |
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ZA (1) | ZA81989B (en) |
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Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1432713A (en) | 1965-02-10 | 1966-03-25 | Novacel Sa | New manufacturing process for pressure-adhering adhesive tapes and device therefor |
US3987037A (en) * | 1971-09-03 | 1976-10-19 | Minnesota Mining And Manufacturing Company | Chromophore-substituted vinyl-halomethyl-s-triazines |
US3779778A (en) * | 1972-02-09 | 1973-12-18 | Minnesota Mining & Mfg | Photosolubilizable compositions and elements |
US4181752A (en) * | 1974-09-03 | 1980-01-01 | Minnesota Mining And Manufacturing Company | Acrylic-type pressure sensitive adhesives by means of ultraviolet radiation curing |
DE2718259C2 (en) | 1977-04-25 | 1982-11-25 | Hoechst Ag, 6000 Frankfurt | Radiation-sensitive mixture |
JPS5928328B2 (en) * | 1977-11-29 | 1984-07-12 | 富士写真フイルム株式会社 | Photopolymerizable composition |
-
1980
- 1980-02-14 US US06/121,404 patent/US4330590A/en not_active Expired - Lifetime
-
1981
- 1981-01-23 WO PCT/US1981/000105 patent/WO1981002262A1/en active IP Right Grant
- 1981-01-23 EP EP81900774A patent/EP0045802B1/en not_active Expired
- 1981-01-23 BR BR8106438A patent/BR8106438A/en unknown
- 1981-01-23 JP JP56501085A patent/JPH0372664B2/ja not_active Expired - Lifetime
- 1981-01-26 CA CA000369335A patent/CA1157998A/en not_active Expired
- 1981-02-11 ES ES499310A patent/ES499310A0/en active Granted
- 1981-02-13 KR KR1019810000450A patent/KR840001929B1/en active
- 1981-02-13 ZA ZA00810989A patent/ZA81989B/en unknown
- 1981-02-13 DE DE3105343A patent/DE3105343A1/en not_active Withdrawn
- 1981-02-13 IT IT47795/81A patent/IT1142313B/en active
Also Published As
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EP0045802A4 (en) | 1982-07-06 |
KR840001929B1 (en) | 1984-10-25 |
US4330590A (en) | 1982-05-18 |
KR830005317A (en) | 1983-08-13 |
DE3105343A1 (en) | 1981-12-10 |
ES8204754A1 (en) | 1982-05-16 |
JPH0372664B2 (en) | 1991-11-19 |
EP0045802B1 (en) | 1985-04-03 |
WO1981002262A1 (en) | 1981-08-20 |
JPS57500106A (en) | 1982-01-21 |
IT1142313B (en) | 1986-10-08 |
EP0045802A1 (en) | 1982-02-17 |
IT8147795A0 (en) | 1981-02-13 |
BR8106438A (en) | 1981-12-29 |
ES499310A0 (en) | 1982-05-16 |
ZA81989B (en) | 1982-03-31 |
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