KR102473112B1 - Uv-curable surface protection film with dot type adhesive layer and method of preparing the same - Google Patents
Uv-curable surface protection film with dot type adhesive layer and method of preparing the same Download PDFInfo
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- KR102473112B1 KR102473112B1 KR1020220137532A KR20220137532A KR102473112B1 KR 102473112 B1 KR102473112 B1 KR 102473112B1 KR 1020220137532 A KR1020220137532 A KR 1020220137532A KR 20220137532 A KR20220137532 A KR 20220137532A KR 102473112 B1 KR102473112 B1 KR 102473112B1
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- KR
- South Korea
- Prior art keywords
- acrylate
- pressure
- sensitive adhesive
- protective film
- weight
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 23
- 239000012790 adhesive layer Substances 0.000 title abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 230000001681 protective effect Effects 0.000 claims abstract description 49
- 239000000853 adhesive Substances 0.000 claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 claims abstract description 37
- 238000005187 foaming Methods 0.000 claims abstract description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 66
- 239000000178 monomer Substances 0.000 claims description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- -1 2-hydroxypropyl Chemical group 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 15
- 229920006243 acrylic copolymer Polymers 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 15
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000006303 photolysis reaction Methods 0.000 claims description 12
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 10
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 claims description 3
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 abstract description 4
- 239000011800 void material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZEERWUUHFUFJJT-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1.CC(C)(O)C(=O)C1=CC=CC=C1 ZEERWUUHFUFJJT-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 235000021109 kimchi Nutrition 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- 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
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
Abstract
Description
본 발명은 도트 형태로 코팅된 자외선 경화형 보호 필름 및 이의 제조방법에 관한 것으로, 더욱 상세하게는, 보호필름에 자외선이 조사되면 광중합성 단량체의 가교와 아조계 화합물의 발포로 인해 점착제층의 접착력이 저하되어 제품으로부터 탈착이 용이한 도트 형태로 코팅된 자외선 경화형 보호 필름 및 이의 제조방법에 관한 것이다. The present invention relates to a UV curable protective film coated in a dot shape and a method for manufacturing the same, and more particularly, when the protective film is irradiated with UV light, the adhesive strength of the pressure-sensitive adhesive layer is increased due to crosslinking of photopolymerizable monomers and foaming of an azo-based compound. It relates to an ultraviolet curable protective film coated in a dot shape that is degraded and easily detached from a product and a method for manufacturing the same.
금속 판재는 다양한 산업 분야에서 사용되고 있는 바, 예를 들면 가전제품(냉장고 등), 건자재 및 자동차에서는 필수적으로 사용되고 있는 중요 소재 중 하나이다. 이러한 금속 판재, 구체적으로 강판은 적용 분야에 따라 다양한 후-가공 프로세스를 거치게 되는데, 적용 분야에 따라 절단 및 절곡과 같은 물리적 변형 과정을 거치게 되며, 또한 보관, 수송 등의 과정을 거치게 된다. 그러나, 금속 판재에 별도의 표면 보호 처리를 하지 않을 경우, 전술한 후-가공 프로세스 과정 중 금속 판재의 표면에 물리적 및/또는 화학적 자극을 받게 되어 결함이 발생한다. 특히, 수출용 금속 판재의 경우, 장기간 보관/운송을 거쳐야 하고, 세관 통관 및 후-가공 지역으로 운송되는 과정 중 많은 물리적 및 화학적 자극을 받게 되어 결함 유발 가능성이 더욱 크다고 할 수 있다.Metal plates are used in various industrial fields, and are, for example, one of the important materials essential for home appliances (refrigerators, etc.), construction materials, and automobiles. These metal plates, specifically steel plates, go through various post-processing processes depending on the field of application. Depending on the field of application, they undergo physical transformation processes such as cutting and bending, and also go through processes such as storage and transportation. However, if a separate surface protection treatment is not applied to the metal sheet, the surface of the metal sheet is subjected to physical and/or chemical stimuli during the above-described post-processing process, resulting in defects. In particular, in the case of metal sheets for export, they have to be stored/transported for a long period of time, and are subjected to many physical and chemical stimuli during the process of customs clearance and transport to post-processing areas, so the possibility of causing defects is greater.
상술한 이유로 인하여, 금속 판재를 제조한 후, 코일 형태로 포장하기에 앞서 이의 표면에 고분자 재질의 보호필름을 부착 또는 적층하여 잠재적인 표면 결함 형성을 방지하고 있다. 최근에는 금속 판재 보호용 필름에 표면 보호 기능뿐만 아니라, 다양한 색상, 문양, 광택 등을 부여하고 있으며, 이는 냉장고, 김치 냉장고, 에어컨 등의 가전제품의 외관에 적용되고 있다.일반적으로, 전자 부품 등에는 표면을 보호하기 위한 점착 보호필름이 부착되고 있다. 이러한 점착 보호필름은 특히 모바일 폰(Mobile phone), 컴퓨터 모니터, TV, 냉장고 및 각종 광고판 등의 표시장치를 구성하는 LCD 패널(LiquidCrystal Display Panel), PDP(Plasma Display Panel) 등과 같은 디스플레이 패널 등에 그 사용이 급증하고 있다For the above reasons, after manufacturing a metal plate, a protective film made of a polymer material is attached or laminated on the surface of the metal plate prior to packaging in a coil form to prevent potential surface defects from forming. Recently, not only the surface protection function but also various colors, patterns, gloss, etc. are given to the metal plate protection film, which is applied to the exterior of home appliances such as refrigerators, kimchi refrigerators, and air conditioners. In general, electronic parts, etc. An adhesive protective film is attached to protect the surface. This adhesive protective film is particularly used for display panels such as LCD panels (Liquid Crystal Display Panels) and PDPs (Plasma Display Panels) constituting display devices such as mobile phones, computer monitors, TVs, refrigerators and various billboards. is soaring
보호필름은 금속 판재 등에 높은 접착력으로 부착되면 절삭 등의 작업중에 금속 판재로부터 벗겨지거나 들뜨지 않아 작업 안정성과 효율을 높일 수 있는 반면, 작업 종료 후에 보호필름을 금속 판재로부터 제거하기가 어려운 문제점이 있었다.When the protective film is attached with high adhesive strength to the metal plate, etc., it is not peeled off or lifted from the metal plate during cutting, etc., thereby increasing work stability and efficiency. However, it is difficult to remove the protective film from the metal plate after work has been completed.
이를 해결하기 위하여 미국등록특허 제5,955,512호에서는 분자량 200,000을 갖는 아크릴공중합체, 광중합용 우레탄아크릴레이트, 아크릴오일 또는 메타크릴오일기를 갖고 있는 광중합이 가능한 조성물, 경화제, 가소제 등을 사용하여 피착제 위에 점착제를 남기지 않고 점착력을 감소시키는 방법을 이용하고 있다. 그러나 상기 방법의 광경화형 점착제의 경우 보호 단면이 작은 웨이퍼 보호용으로 사용하기에 큰 어려움이 없으나, 보호 단면이 넓은 냉장고 등 금속 판재와 같은 경우 광조사후 점착력이 획기적으로 감소되지 않는 경우 보호필름 제거를 위해 여전히 여러 명의 작업 인력이 함께 작업하여야 한다는 문제점이 있었다.To solve this problem, US Patent No. 5,955,512 discloses an acrylic copolymer having a molecular weight of 200,000, urethane acrylate for photopolymerization, a photopolymerizable composition having an acrylic oil or methacrylic oil group, a curing agent, a plasticizer, etc. It uses a method to reduce the adhesive force without leaving behind. However, in the case of the photocurable adhesive of the above method, there is no great difficulty in using it for protecting wafers with a small protective cross section, but in the case of metal plates such as refrigerators with a wide protective cross section, if the adhesive strength is not significantly reduced after light irradiation To remove the protective film There was still a problem that several working personnel had to work together.
본 발명은 작업 후에 금속판재에 부착된 필름을 용이하게 제거할 수 있는 자외선 경화형 보호필름을 제공하는 것이다.The present invention is to provide an ultraviolet curable protective film that can easily remove the film attached to the metal sheet after operation.
일구현예에서, 본 발명은In one embodiment, the present invention
탄소원자수 1~14개인 알킬기를 갖는 아크릴 단량체, 비닐계 단량체, 열경화성 개시제를 용매에 혼합하는 단계 ;mixing an acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a vinyl monomer, and a thermosetting initiator in a solvent;
상기 혼합용액을 열중합하는 아크릴 공중합체 제조단계 ;Preparing an acrylic copolymer by thermally polymerizing the mixed solution;
제조된 상기 아크릴 공중합체 용액에 광중합성 모노머, 광개시제 및 아조계 화합물을 혼합하는 점착제 조성물 제조단계 ;A pressure-sensitive adhesive composition preparation step of mixing a photopolymerizable monomer, a photoinitiator, and an azo-based compound with the prepared acrylic copolymer solution;
상기 점착제 조성물을 기재필름 상에 코팅하여 건조시키는 점착제층 형성단계를 포함하고,A pressure-sensitive adhesive layer forming step of coating the pressure-sensitive adhesive composition on a base film and drying it,
상기 점착제층 형성단계는 상기 점착제 조성물을 홀이 형성된 드럼을 사용하여 도트(dot) 형태로 인쇄하는 단계 및 이를 건조하는 단계를 포함하고, The step of forming the pressure-sensitive adhesive layer includes printing the pressure-sensitive adhesive composition in a dot form using a drum having holes and drying the pressure-sensitive adhesive composition,
상기 아크릴 공중합체 제조단계는 The step of preparing the acrylic copolymer is
아크릴 단량체 100중량부 대비 비닐계 단량체 5~10중량부, 열경화성 개시제 0.1~2중량부를 용매에 넣어 혼합한 후 열중합으로 제조하고,5 to 10 parts by weight of a vinyl monomer and 0.1 to 2 parts by weight of a thermosetting initiator are mixed in a solvent based on 100 parts by weight of an acrylic monomer, and then prepared by thermal polymerization,
상기 아크릴 단량체는 메틸아크릴레이트, 에틸아크릴레이트, 부틸아크릴레이트, 2-에틸부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 헥실아크릴레이트이고, The acrylic monomer is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate or hexyl acrylate,
상기 비닐계 단량체는 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-하이드록시헥실(메트)아크릴레이트, 2-하이드록시에틸렌글리콜(메트)아크릴레이트 또는 2-하이드록시프로필렌글리콜(메트)아크릴레이트이고,The vinyl-based monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2 -Hydroxyethylene glycol (meth)acrylate or 2-hydroxypropylene glycol (meth)acrylate,
상기 광중합성 모노머는 트리메틸올프로판 트리아크릴레이트(TMPTA), 폴리에틸렌글리콜 디아크릴레이트, 에틸렌옥사이드 부가형 트리메틸올프로판트리아크릴레이트, 에톡시 부가형트리에틸올프로판 트리아크릴레이트, 펜타에리스리톨 테트라아크릴레이트(PETA), 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트 및 이들의 혼합물로 이루어지는 군으로부터 선택되는 1종 이상이고, The photopolymerizable monomer is trimethylolpropane triacrylate (TMPTA), polyethylene glycol diacrylate, ethylene oxide addition type trimethylolpropane triacrylate, ethoxy addition type triethylolpropane triacrylate, pentaerythritol tetraacrylate (PETA) , 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and at least one selected from the group consisting of mixtures thereof,
상기 아조계 화합물이 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 2,2-아조비스(2,4-디메틸발레로니트릴), 2,2-아조비스이소부티로니트릴, 디메틸 2,2-아조비스이소부티레이트, 2,2-아조비스(2-메틸부티로니트릴), 1,1-아조비스(1-시클로헥산카보니트릴) 및 2,2-아조비스(2,4,4-트리메틸펜탄)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 자외선 경화형 보호 필름의 제조방법에 관련된다.The azo-based compound is 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis Isobutyronitrile, dimethyl 2,2-azobisisobutyrate, 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(1-cyclohexanecarbonitrile) and 2,2-azo It relates to a method for manufacturing an ultraviolet curable protective film, characterized in that at least one selected from the group consisting of bis (2,4,4-trimethylpentane).
다른 구현예에서, 본 발명은 상기 제조방법으로 제조된 자외선 경화형 보호 필름에 관련된다.In another embodiment, the present invention relates to an ultraviolet curable protective film prepared by the above manufacturing method.
본 발명은 점착제 조성물을 기재 필름상에 전면을 코팅한 것이 아니라 도트(dot) 형태로 코팅하거나 접착제층에 칼집(일종의 틈임)을 형성하여(결과적으로 접착제층과 피보호 대상물과의 사이에 (미접착된) 공극이 존재함) 보호필름의 탈착력을 낮출 수 있다. The present invention does not coat the entire surface of the adhesive composition on the base film, but rather coats it in a dot form or forms a sheath (a kind of gap) in the adhesive layer (as a result, between the adhesive layer and the object to be protected (not Adhered) voids exist) may lower the detachability of the protective film.
또한, 본 발명의 자외선 경화형 보호필름은 접착제층과 피보호 대상물과의 사이의 공극(틈)이 점착제층 내부에서 발포 기체를 이송 및 배출하는 경로를 제공할 수 있고, 결과적으로 접착층 내부의 압력 증가를 해소시켜 발포제로부터 기체 발생을 좀 더 활발하게 할 수 있다.In addition, in the ultraviolet curable protective film of the present invention, the gap (gap) between the adhesive layer and the object to be protected can provide a path for transporting and discharging foaming gas from the inside of the adhesive layer, and as a result, the pressure inside the adhesive layer increases. , it is possible to more actively generate gas from the foaming agent.
본 발명의 자외선 경화형 보호 필름 제조방법은 광중합성 모노머, 광개시제, 아조계 발포제와 발포용 촉매를 포함하여 한 번의 자외선 조사로 광중합성 모노머를 중합시킴과 동시에 기체를 발포시켜 점착제층의 접착력을 크게 저하시킬 수 있다.The manufacturing method of the UV-curable protective film of the present invention polymerizes the photopolymerizable monomer with a single ultraviolet irradiation, including a photopolymerizable monomer, a photoinitiator, an azo foaming agent, and a foaming catalyst, and at the same time foams the gas to greatly reduce the adhesive strength of the pressure-sensitive adhesive layer. can make it
또한, 본 발명의 자외선 경화형 보호 필름 제조방법은 자외선 조사와 발포를 동시에 진행하여 작업 공정을 단축시킬 수 있다.In addition, the manufacturing method of the UV curable protective film of the present invention can shorten the work process by simultaneously proceeding with UV irradiation and foaming.
도 1은 본 발명의 자외선 경화형 보호 필름의 단면 구조를 나타낸다.
도 2는 도 1의 보호필름에서 도트 형태로 점착제층이 기재 필름에 코팅된 단면 구조이다. 1 shows the cross-sectional structure of an ultraviolet curable protective film of the present invention.
FIG. 2 is a cross-sectional structure in which a dot-shaped adhesive layer is coated on a base film in the protective film of FIG. 1 .
본 발명은 하기의 설명에 의하여 모두 달성될 수 있다. 하기의 설명은 본 발명의 바람직한 구체예를 기술하는 것으로 이해되어야 하며, 본 발명이 반드시 이에 한정되는 것은 아니다. 또한, 첨부된 도면은 이해를 돕기 위한 것으로, 본 발명이 이에 한정되는 것은 아니며, 개별 구성에 관한 세부 사항은 후술하는 관련 기재의 구체적 취지에 의하여 적절히 이해될 수 있다.The present invention can all be achieved by the following description. The following description should be understood as describing preferred embodiments of the present invention, but the present invention is not necessarily limited thereto. In addition, the accompanying drawings are for understanding, and the present invention is not limited thereto, and details of individual components can be properly understood by the specific purpose of the related description to be described later.
본 명세서에서 사용되는 용어는 하기와 같이 정의될 수 있다.Terms used in this specification may be defined as follows.
"보호 필름"은, 스텐레스, PCM, VCM, PET칼라강판, 알루미늄 강판, 특수 선박 내장재 및 방화문, 냉장고, 세탁기 컬러 가전뿐만 아니라 디스플레이 디바이스를 외부의 물리적 또는 화학적 자극으로부터 보호하는 필름을 의미할 수 있다."Protective film" may refer to a film that protects stainless steel, PCM, VCM, PET color steel plate, aluminum steel plate, special ship interior materials and fire doors, refrigerators, washing machines, color home appliances, as well as display devices from external physical or chemical stimuli. .
"아크릴계"라는 용어는 폴리메타크릴레이트와 같이 아크릴산으로부터 유도된 고분자 및 단량체를 포함하는 것으로 해석될 수 있다.The term "acrylic" may be interpreted to include polymers and monomers derived from acrylic acid, such as polymethacrylate.
"점착제"는 실온 부근의 온도 영역에서 부드러운 고체(점탄성체) 상태를 나타내고, 압력에 의하여 피착체에 접착하는 성질을 갖는 재료를 의미할 수 있는 바, 예를 들면, 복소 인장 탄성률 E*(1Hz) < 107 dyne/㎠(25℃)를 만족하는 물성을 나타낼 수 있다.“Adhesive” may refer to a material that exhibits a soft solid (viscoelastic) state in a temperature region around room temperature and has a property of adhering to an adherend by pressure, for example, the complex tensile modulus E* (1Hz ) < 107 dyne/cm2 (25°C).
어떠한 구성요소를 "포함"한다고 할 때, 이는 별도의 언급이 없는 한, 다른 구성 요소 및/또는 단계를 더 포함할 수 있음을 의미한다.When it is said that a certain component is "included", it means that it may further include other components and / or steps unless otherwise stated.
일 부재가 다른 부재 "위에" 또는 "아래에" 있는 경우, 이는 다른 부재 "바로 위에" 또는 "바로 아래에"있는 경우뿐만 아니라, 그 중간에 또 다른 부재가 개재되어 있는 경우도 포함할 수 있다. 반대로, 일 부재가 다른 부분 "바로 위에" 또는 "바로 아래에" 있다고 할 때에는 중간에 다른 부분이 없는 것을 의미할 수 있다.When one member is “above” or “below” another member, this may include not only the case where another member is “directly above” or “directly below” another member, but also the case where another member is interposed therebetween. . Conversely, when a member is said to be “directly over” or “directly below” another part, it may mean that there is no other part in the middle.
이하, 첨부된 도면을 참조하여 본 발명을 설명하기로 한다.Hereinafter, the present invention will be described with reference to the accompanying drawings.
도 1은 본 발명의 자외선 경화형 보호 필름의 단면 구조를 나타내고, 도 2는 도 1의 보호필름에서 도트 형태로 점착제층이 기재 필름에 코팅된 단면 구조이다.1 shows a cross-sectional structure of an ultraviolet curable protective film of the present invention, and FIG. 2 is a cross-sectional structure in which a dot-shaped adhesive layer is coated on a base film in the protective film of FIG. 1.
본 발명의 자외선 경화형 보호필름 제조방법은 혼합단계, 아크릴 공중합체 제조단계, 점착제 조성물 제조단계 및 건조단계를 포함한다.The manufacturing method of the UV-curable protective film of the present invention includes a mixing step, an acrylic copolymer manufacturing step, an adhesive composition manufacturing step, and a drying step.
상기 혼합단계는 탄소원자수 1~14개인 알킬기를 갖는 아크릴 단량체, 비닐계 단량체, 열경화성 개시제를 용매에 혼합하는 단계이다. The mixing step is a step of mixing an acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a vinyl monomer, and a thermosetting initiator in a solvent.
상기 탄소원자수 1~14개인 알킬기를 갖는 아크릴 단량체는 메틸(메타)아크릴레이트， 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트， 부틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 핵실(메타)아크릴레이트, 2-에틸핵실(메타)아크릴레이트, 에틸부틸(메타)아크릴레이트， 옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소노닐(메타)아크릴레이트, 라우릴(메타)아크릴레이트 및/또는 테트라데실(메타)아크릴레이트 등일 수 있다.The acrylic monomer having an alkyl group having 1 to 14 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, butyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethylbutyl (meth)acrylate, octyl (meth)acrylic rate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and/or tetradecyl (meth)acrylate, and the like.
상기 비닐계 단랑체는 가교성 관능기를 함유하는 개질용 공단량체일 수 있다. 상기 비닐계 단량체의 예로는 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-하이드록시헥실(메트)아크릴레이트, 2-하이드록시에틸렌글리콜(메트)아크릴레이트 또는 2-하이드록시프로필렌글리콜(메트)아크릴레이트일 수 있다.The vinyl-based monomer may be a comonomer for modification containing a crosslinkable functional group. Examples of the vinyl monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. , 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate.
상기 비닐계 단량체는 상기 아크릴 단량체 100중량부 대비 약 1 내지 10 중량부, 구체적으로 약 5 내지 10 중량부로 첨가 또는 사용될 수 있다. 상기 비닐계 단량체가 5중량부 초과인 것이 적정의 응집력을 가져 재박리성이 향상되고, 10 중량부 초과이면 가교도가 증가하여 점착층의 젖음성이 떨어질 구 있다. The vinyl-based monomer may be added or used in an amount of about 1 to 10 parts by weight, specifically about 5 to 10 parts by weight, based on 100 parts by weight of the acrylic monomer. When the amount of the vinyl-based monomer is greater than 5 parts by weight, re-peelability is improved due to appropriate cohesive force, and when the content is greater than 10 parts by weight, the degree of crosslinking is increased and the wettability of the adhesive layer is deteriorated.
상기 열경화형 개시제로 아조비스이소부티로니트릴, 아조비스시클로헥산카르보니트릴이 사용될 수 있다. 상기 열경화형 개시제는 상기 아크릴 단량체 100중량부 대비 약 0.1 내지 2중량부로 첨가 또는 사용될 수 있다.As the thermosetting initiator, azobisisobutyronitrile and azobiscyclohexanecarbonitrile may be used. The thermosetting initiator may be added or used in an amount of about 0.1 to 2 parts by weight based on 100 parts by weight of the acrylic monomer.
상기 용매는 톨루엔, 알코올, 에틸아세테이트 또는 메틸에틸케톤 일 수 있다. 상기 용매는 상기 아크릴 단량체 100중량부 대비 100중량부 내지 300중량부일 수 있으며, 바람직하게는 100중량부 내지 200중량부 내에서 적절히 조절될 수 있다. The solvent may be toluene, alcohol, ethyl acetate or methyl ethyl ketone. The solvent may be 100 parts by weight to 300 parts by weight based on 100 parts by weight of the acrylic monomer, and preferably may be appropriately adjusted within 100 parts by weight to 200 parts by weight.
상기 아크릴 공중합체 제조단계는 상기 혼합용액을 열중합시켜 공중합체를 제조하는 단계이다. 이러한 아크릴계 고분자는 용액중합법, 광중합법, 벌크 중합법, 서스펜션중합법, 또는 에멀젼중합법 등의 방법으로 제조할 수 있으며, 보다 구체적으로는 용액 중합법으로 제조 가능하다. 이때, 중합온도는, 예를 들면 약 50 내지 140℃, 구체적으로 약 70 내지 120℃ 범위일 수 있고, 필요 시 단량체가 균일하게 혼합된 상태에서 상기 열결화형 개시제를 첨가하여 중합시킬 수 있다.The step of preparing the acrylic copolymer is a step of preparing a copolymer by thermally polymerizing the mixed solution. Such an acrylic polymer may be prepared by a method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and more specifically, solution polymerization. At this time, the polymerization temperature may be, for example, about 50 to 140 ° C., specifically about 70 to 120 ° C., and if necessary, polymerization may be performed by adding the thermosetting initiator in a state in which monomers are uniformly mixed.
제조된 아크릴계 공중합체는 중량평균 분자량이 100,000 내지 1,000,000일 수 있다.The prepared acrylic copolymer may have a weight average molecular weight of 100,000 to 1,000,000.
‘ 상기 점착제 조성물 제조단계는 제조된 상기 아크릴 공중합체 용액에 광중합성 모노머, 광개시제 및 아조계 화합물을 혼합하는 단계이다. ‘The pressure-sensitive adhesive composition preparation step is a step of mixing a photopolymerizable monomer, a photoinitiator, and an azo-based compound with the prepared acrylic copolymer solution.
상기 광중합성 모노머는 분자 구조내 하나 이상의 아크릴레이트기, 메타크릴레이트 또는 비닐기를 포함하는 구조를 가진다. The photopolymerizable monomer has a structure including at least one acrylate, methacrylate or vinyl group in its molecular structure.
예를 들면, 상기 광중합성 모노머는 트리메틸올프로판 트리아크릴레이트(TMPTA), 폴리에틸렌글리콜 디아크릴레이트, 에틸렌옥사이드 부가형 트리메틸올프로판트리아크릴레이트, 에톡시 부가형트리에틸올프로판 트리아크릴레이트, 펜타에리스리톨 테트라아크릴레이트(PETA), 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트, 에톡실레이티드 펜타에리스리톨 테트라아크릴레이트, 2-페녹시에틸아크릴레이트, 에톡실레이티드 비스페놀 A 디아크릴레이트 및 이들의 혼합물로 이루어지는 군으로부터 선택되는 1종 이상일 수 있다. For example, the photopolymerizable monomer is trimethylolpropane triacrylate (TMPTA), polyethylene glycol diacrylate, ethylene oxide addition type trimethylolpropane triacrylate, ethoxy addition type triethylolpropane triacrylate, pentaerythritol tetraacryl Latex (PETA), 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylated pentaerythritol tetraacrylate, 2-phenoxyethyl acrylate, ethoxylated bisphenol A diacrylate rate and at least one selected from the group consisting of mixtures thereof.
상기 광중합성 모노머는 상기 아크릴(레이트) 단량체 100중량부 대비 10~20중량부가 사용될 수 있다. 상기 광중합성 모노머의 함량이 10중량부 미만인 경우에는 광중합에 의한 3차원 망상구조가 점착제층 전체에 걸쳐 균일하게 형성되기 어려우며, 20중량부를 초과하는 경우에는 아크릴 공중합체의 상대적 함량이 줄어들어 초기 점착력이 떨어지고 또한, 자외선 조사 시간이 증가하여 작업 공정이 지연될 수 있다.The photopolymerizable monomer may be used in an amount of 10 to 20 parts by weight based on 100 parts by weight of the acrylic (late) monomer. When the content of the photopolymerizable monomer is less than 10 parts by weight, it is difficult to uniformly form a three-dimensional network structure by photopolymerization over the entire pressure-sensitive adhesive layer, and when it exceeds 20 parts by weight, the relative content of the acrylic copolymer is reduced, so that the initial adhesive strength In addition, the UV irradiation time may increase and the work process may be delayed.
상기 광개시제는 자외선 에너지에 의해 라디칼 형태가 되고 이들 라디칼이 수지내의 이중결합을 공격함으로써 중합을 유도하는 역할을 한다.The photoinitiator is in the form of radicals by ultraviolet energy, and these radicals attack double bonds in the resin to induce polymerization.
상기 광개시제로는 상업적으로 수득가능한 Irgacure#184(히드록시시클로헥실 페닐 케톤(hydroxycyclohexylphenylketone)), Irgacure#907(2-메틸-1[4-(메틸티오)페닐]-2-모폴리노-프로판-1-on(2-methyl-1[4-(methythio)phenyl]-2-morpholino-propan-1-on)), Irgacure#500, Irgacure#651, Darocure#1173(2-히드록시-2-메틸-1-페닐-프로판-1-온(2-hydroxy-2-methyl-1-phenyl-propan-1-one)), Darocure#116, CGI#1800 및 CGI#1700 등이 있다. As the photoinitiator, commercially available Irgacure #184 (hydroxycyclohexylphenylketone), Irgacure #907 (2-methyl-1 [4- (methylthio) phenyl] -2-morpholino-propane- 1-on(2-methyl-1[4-(methythio)phenyl]-2-morpholino-propan-1-on)), Irgacure#500, Irgacure#651, Darocure#1173(2-hydroxy-2-methyl -1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one), Darocure #116, CGI #1800 and CGI #1700.
상기 광개시제는 상기 아크릴(레이트) 단량체 100중량부 대비 1~5중량부가 사용될 수 있다. The photoinitiator may be used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic (late) monomer.
아조계 화합물은 200 내지 300nm의 자외선 파장대에서 분해되는 물질로서, 개시제로 사용하면 광분해에 의해 부산물로 기체를 발생하므로 점착층 내부 또는 점착제층과 피보호 대상물 사이에 미세기공을 형성시킬 수 있다.Azo-based compounds are substances that decompose in the ultraviolet wavelength range of 200 to 300 nm, and when used as an initiator, gas is generated as a by-product by photolysis, so micropores can be formed inside the adhesive layer or between the adhesive layer and the object to be protected.
상기 아조계 화합물은 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 2,2-아조비스(2,4-디메틸발레로니트릴), 2,2-아조비스이소부티로니트릴, 디메틸 2,2-아조비스이소부티레이트, 2,2-아조비스(2-메틸부티로니트릴), 1,1-아조비스(1-시클로헥산카보니트릴), 2-(카바모일아조)-이소부티로니트릴, 2,2-아조비스(2,4,4-트리메틸펜탄), 2,2-아조비스(N,N-디메틸렌이소부틸아미딘)디하이드로클로라이드, 2,2-아조비스(2-아미노프로판)디하이드로클로라이드, 2,2-아조비스(N,N-디메틸렌이소부틸아미드), 4, 4-아조비스[2-메틸-N-(2-하이드록실)프로피온아미드], 아조벤젠, 아조비스-3급-부탄으로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.The azo-based compound is 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis Isobutyronitrile, dimethyl 2,2-azobisisobutyrate, 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(1-cyclohexanecarbonitrile), 2-(carbamoyl) Azo) -isobutyronitrile, 2,2-azobis (2,4,4-trimethylpentane), 2,2-azobis (N, N-dimethylene isobutylamidine) dihydrochloride, 2,2 -Azobis(2-aminopropane)dihydrochloride, 2,2-azobis(N,N-dimethyleneisobutylamide), 4,4-azobis[2-methyl-N-(2-hydroxyl) propionamide], azobenzene, and azobis-tert-butane.
상기 아조계 화합물은 상기 아크릴 단량체 100중량부 대비 1~10중량부, 바람직하게는 1 내지 5중량부가 사용될 수 있다. 상기 아조계 화합물이 10중량부를 초과하면 상기 점착제 조성물 내에서 용해도가 떨어져 석츨될 수 있고, 1중량부 미만이면 원하는 발포 효과(보호필름의 탈착력 저하)를 얻을 수 없다.The azo-based compound may be used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the acrylic monomer. If the azo-based compound exceeds 10 parts by weight, the solubility in the pressure-sensitive adhesive composition may be reduced and may precipitate, and if it is less than 1 part by weight, a desired foaming effect (decreased desorption force of the protective film) may not be obtained.
한편, 상기 아조계 발포 물질이 5중량부 내지 10중량부 범위로 사용되는 경우 초기에는 점착제 조성물(또는 점착제층) 내에서 용해되지만, 시간 경과에 따라 용매 증발 현상이나 온도 감소로 용해도가 떨어져 석츨되는 문제가 있었다. On the other hand, when the azo-based foam material is used in the range of 5 parts by weight to 10 parts by weight, it is initially dissolved in the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer), but over time, the solubility decreases due to solvent evaporation or temperature decrease and precipitates. There was a problem.
상기 아조계 발포 물질이 1중량부 내지 5중량부 범위로 사용되는 경우. 용해도 저하에 따른 석출 문제는 해소될 수 있으나 냉장고 등에 사용되는 금속 판재의 보호 필름의 탈착력 저하에는 한계가 있었다. 점 더 상세하게는, 금속 판재 보호 필름은 일반적으로 반도체 제조공정용 다이싱 테이프(또는 반도체 패키지 작용용 보호 필름)에 비해 사용되는 필름의 면적(단면)이 수배 내지 수십 배 이상 크고, 따라서, 상기 아조계 발포 물질이 1중량부 내지 5중량부 범위로 사용되는 경우 다이싱 테이프(보호필름)의 탈착력 저하에 효과가 있으나, 면적이 넓어 더 많은 탈착힘이 요구되는 금속 판재용 보호필름을 효과적으로 탈착시키기에는 다소 한계가 있었다.When the azo-based foaming material is used in the range of 1 part by weight to 5 parts by weight. The precipitation problem due to the decrease in solubility can be solved, but there is a limit to the decrease in the detachability of the protective film of the metal plate used in the refrigerator. In more detail, the area (cross-section) of the metal sheet protective film is several times to several tens of times larger than that of the dicing tape for the semiconductor manufacturing process (or the protective film for semiconductor packaging). When the azo-based foaming material is used in the range of 1 part by weight to 5 parts by weight, it is effective in reducing the detachability of the dicing tape (protective film), but it is effective in reducing the detachability of the dicing tape (protective film). Desorption had some limitations.
본 발명의 상기 점착제 조성물 제조단계는 상기 아조계 화합물의 반응을 촉진하는 광분해 촉매를 추가로 포함할 수 있다. 상기 광분해 촉매로는 코발트(II) 아세테이트, 구리(II) 아세테이트 등이 사용될 수 있다. The step of preparing the pressure-sensitive adhesive composition of the present invention may further include a photolysis catalyst that promotes the reaction of the azo-based compound. Cobalt (II) acetate, copper (II) acetate, and the like may be used as the photolysis catalyst.
상기 광분해 촉매는 상기 아크릴 단량체 100중량부 대비 0.5 내지 2중량부, 바람직하게는 0.5 내지 1중량부가 사용될 수 있다. 상기 광반응 촉매가 이보다 과량 첨가되면 수지 조성물이 상온에서 겔화되거나 구리가 석출될 수 있다.The photolysis catalyst may be used in an amount of 0.5 to 2 parts by weight, preferably 0.5 to 1 part by weight, based on 100 parts by weight of the acrylic monomer. If the photoreaction catalyst is added in excess, the resin composition may be gelled at room temperature or copper may be precipitated.
후술하는 바와 같이, 상기 광분해 촉매가 상기 아조계 발포 물질(1중량부 내지 5중량부 범위)과 함께 사용되는 경우에 다이싱 테이프(보호필름)의 탈착력이 10gf/㎠ 이하로 현저히 저하될 수 있었다.As will be described later, when the photolysis catalyst is used together with the azo-based foaming material (in the range of 1 part by weight to 5 parts by weight), the detachability of the dicing tape (protective film) can be significantly lowered to 10 gf/cm 2 or less. there was.
상기 점착제 조성물의 점도(25℃)는, 예를 들면 약 3,000 내지 6,000 cps, 구체적으로 약 3,500 내지 5,500 cps, 보다 구체적으로 약 4,000 내지 5,000 cps 범위일 수 있다. 상기 유기 용매는 추후 건조 과정을 통하여 휘발될 수 있다. 다만, 점착제 조성물의 점도가 지나치게 낮은 경우에는 후술하는 코팅(도포) 과정 및 점착제 코팅 필름 기재의 이송 과정에서 흘러내리는 현상이 발생할 수 있고, 또한 점착제 조성물의 점도가 지나치게 높은 경우에는 필름 기재 상에 균일하게 코팅하기 곤란할 수 있다.The viscosity (25° C.) of the pressure-sensitive adhesive composition may be, for example, about 3,000 to 6,000 cps, specifically about 3,500 to 5,500 cps, and more specifically about 4,000 to 5,000 cps. The organic solvent may be volatilized through a drying process later. However, when the viscosity of the pressure-sensitive adhesive composition is too low, a phenomenon of flowing down may occur during the coating (coating) process described later and during the transfer process of the pressure-sensitive adhesive coated film substrate, and when the viscosity of the pressure-sensitive adhesive composition is excessively high, uniformity on the film substrate It can be difficult to coat properly.
본 발명의 자외선 경화형 보호 필름의 제조방법은 상기 점착제 조성물을 기재 필름상에 코팅하여 건조시키는 단계를 포함할 수 있다.The manufacturing method of the UV-curable protective film of the present invention may include coating and drying the pressure-sensitive adhesive composition on a base film.
상기 기재필름은 PE, PP, CPP일 수 있다.The base film may be PE, PP, or CPP.
기재필름 상에 코팅된 점착제 조성물의 건조 온도는, 예를 들면 약 50 내지 180℃, 구체적으로 약 60 내지 120℃, 보다 구체적으로 약 70 내지 100℃ 범위일 수 있는 바, 이는 사용되는 유기 용매에 따라 변화 가능하다.The drying temperature of the pressure-sensitive adhesive composition coated on the base film may be, for example, about 50 to 180 ° C, specifically about 60 to 120 ° C, more specifically about 70 to 100 ° C, which depends on the organic solvent used. can change according to
상기 조성물이 건조된 점착제층은, 예를 들면 약 10 내지 100g/㎡, 구체적으로 약 30 내지 80g/㎡, 보다 구체적으로 약 40 내지 70g/㎡의 평량 범위를 가질 수 있다. 또한, 점착제층(12)의 두께(건조 후 두께)는, 예를 들면 약 10 내지 40㎛, 구체적으로 약 15내지 35㎛, 보다 구체적으로 약 20 내지 30㎛ 범위 내에서 조절될 수 있다.The pressure-sensitive adhesive layer in which the composition is dried may have a basis weight range of, for example, about 10 to 100 g/m 2 , specifically about 30 to 80 g/m 2 , and more specifically about 40 to 70 g/m 2 . In addition, the thickness of the pressure-sensitive adhesive layer 12 (thickness after drying) may be adjusted within a range of, for example, about 10 to 40 μm, specifically about 15 to 35 μm, and more specifically about 20 to 30 μm.
도 1을 참고하면, 상기 점착제 조성물을 기재필름 상에 코팅하는 단계는 기재 필름(10) 상에 코터를 통해 점착제 조성물을 균일하게 도포하고, 그 위에 이형지(30)를 부착할 수 있다. Referring to FIG. 1 , in the step of coating the pressure-sensitive adhesive composition on the base film, the pressure-sensitive adhesive composition may be uniformly applied on the
도 2를 참고하면, 상기 점착제 조성물을 기재필름 상에 코팅하는 단계는 상기 점착제 조성물을 홀(24)이 형성된 드럼(23)을 사용하여 도트(dot) 형태로 코팅하는 단계일 수 있다. 상기 드럼은 홀(음각, 또는 홀 형태 무늬)이 형성된 원통형 동판일 수 있다. Referring to FIG. 2 , the step of coating the pressure-sensitive adhesive composition on the base film may be a step of coating the pressure-sensitive adhesive composition in a dot shape using a
상기 코팅 단계는 동판을 점착제 조성물 용액에 침지시키거나 동판에 조성물 용액을 주입하여 홀에 점착제 조성물을 채우고, 상기 동판을 기재필름 상에 눌러 조성물을 상기 기재 필름상에 전사시킬 수 있다. 상기 코팅 단계는 공지된 그라비아 인쇄 방식을 활용할 수 있다. In the coating step, the copper plate may be immersed in the pressure-sensitive adhesive composition solution or the copper plate may be injected with the composition solution to fill the hole with the pressure-sensitive adhesive composition, and the copper plate may be pressed onto the base film to transfer the composition onto the base film. The coating step may utilize a known gravure printing method.
상기 동판에 홀이 소정 간격으로 이격 형성되는 경우, 상기 점착제 조성물이 상기 기재상에 도트(dot) 형태로 코팅될 수 있다.When holes are formed in the copper plate at predetermined intervals, the pressure-sensitive adhesive composition may be coated on the substrate in a dot form.
상기 도트 형태 코팅은 상기 점착제 조성물이 기재 필름 전면에 걸쳐 코팅되지 않고 섬(island)(20) 형태로 기재 필름상에 소정 간격으로 코팅되는 방식일 수 있다. 또는, 상기 도트 형태 코팅은 상기 점착제 조성물이 격자 형태로 기재 필름상에 소정 간격으로 코팅되는 방식일 수 있다. The dot-shaped coating may be a method in which the pressure-sensitive adhesive composition is coated on the base film at predetermined intervals in the form of
도 2a를 참고하면, 상기 점착제의 도트(dot)(20) 크기는 직경(a)이 5~30mm, 도트 사이 간격(b)은 10㎛~2mm일 수 있다. Referring to FIG. 2A , the size of the
도 2를 참고하면, 도트와 도트 사이에는 공극(21)이 형성되고, 상기 공극은 점착제 조성물이 코팅되지 않은 영역이다. Referring to FIG. 2 , voids 21 are formed between dots, and the voids are regions not coated with the pressure-sensitive adhesive composition.
도 2b의 보호필름에서 이형지(30)를 제거한 후 금속 강판 등 피보호 대상물에 접착제층(20)을 도 2c와 같이 부착할 수 있다.After removing the
종래에는 점착제 조성물이 기재필름 전면에 코팅되는데, 본 발명에서의 도트 방식은 기재 필름 일부에만 코팅되고, 코팅되지 않은 공극(21, 틈, 빈 공간)이 점착제층과 피보호 대상물 사이의 계면에 존재하므로 탈착력을 감소시킬 수 있다. Conventionally, the adhesive composition is coated on the entire surface of the base film, but in the dot method in the present invention, only a portion of the base film is coated, and uncoated voids (21, gaps, empty spaces) exist at the interface between the adhesive layer and the object to be protected. Therefore, the desorption force can be reduced.
좀 더 자세하게는, 상기 점착제의 도트 크기가 5~30mm 범위로 크고, 이들 사이 간격이 10㎛~2mm 범위로 작은 경우 보호필름의 초기 접착력이 현저히 떨어지지 않으면서도 이에 비해 상대적으로 탈착력 저하는 증가하였다. More specifically, when the dot size of the adhesive is large in the range of 5 to 30 mm and the gap between them is small in the range of 10 μm to 2 mm, the initial adhesive strength of the protective film is not significantly lowered, but the desorption strength is relatively increased. .
앞에서 상술한 바와 같이, 본 발명의 보호필름은 상기 아조계 발포 물질이 1중량부 내지 5중량부 범위로 사용되는 경우 다이싱 테이프(보호필름)의 탈착력 저하에 효과가 있으나, 본 발명의 보호필름이 사용되는 금속 판재용 (보호필름)으로 사용되는 경우에는 탈착을 위해 다수의 인력이 여전히 필요하였으며, 이러한 문제를 해결하기 위해, 본 발명에서는 광분해 촉매를 추가로 사용하였다.As described above, the protective film of the present invention is effective in reducing the detachability of the dicing tape (protective film) when the azo-based foam material is used in the range of 1 to 5 parts by weight, but the protective film of the present invention When the film is used as a metal plate material (protective film), a large number of manpower is still required for desorption, and in order to solve this problem, a photolysis catalyst is additionally used in the present invention.
한편, 본 발명의 발명자는 상기 아조계 발포 물질이 1중량부 내지 5중량부 범위로 사용되는 경우에 광분해 촉매를 추가로 사용하지 않는 경우에도 도 2과 같이, 점착제층과 피보호 대상물 계면에 공극(21)을 형성시켜 주면 발포 효율을 좀 더 높일 수 있음을 발견하였다. 즉, 점착제층과 피보호 대상물 계면에 형성된 공극(21)은 점착제층 내부에서 발포 기체를 이송 및 배출하는 경로를 제공할 수 있고, 결과적으로 접착층 내부의 압력 증가를 해소시켜 발포제로부터 기체 발생을 좀 더 활발하게 할 수 있다.On the other hand, the inventors of the present invention, when the azo-based foam material is used in the range of 1 part by weight to 5 parts by weight, even when a photolysis catalyst is not additionally used, as shown in FIG. (21) was found to further increase the foaming efficiency. That is, the
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하지만, 본 발명이 이들 예로만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited only to these examples.
실시예 1Example 1
아크릴계 공중합체 제조Manufacture of acrylic copolymer
2-에틸헥실아크릴레이트 200g, 에틸아크리레이트 200g, 2-히드록시에틸 (메타)아크릴레이트 30g, AIBN 3g을 에틸아세테이트 600g에 넣어 혼합하였다. 중합반응기에서 질소 충진 후 90℃로 가열하여 4시간 동안 반응시켜 아크릴계 공중합체 용액을 수득하였다. 200 g of 2-ethylhexyl acrylate, 200 g of ethyl acrylate, 30 g of 2-hydroxyethyl (meth)acrylate, and 3 g of AIBN were added to 600 g of ethyl acetate and mixed. After filling with nitrogen in a polymerization reactor, the mixture was reacted for 4 hours by heating to 90° C. to obtain an acrylic copolymer solution.
점착제 조성물의 제조Preparation of pressure-sensitive adhesive composition
위에서 제조된 아크릴계 공중합체 용액에 트리메틸올프로판 트리아크릴레이트(TMPTA) 60g, 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴) 5g, Irgacure-184(1-hydroxy cyclohexyl phenyl ketone) 3g을 넣은 후 교반하여 점착제 조성물을 제조하였다. In the acrylic copolymer solution prepared above, 60 g of trimethylolpropane triacrylate (TMPTA), 5 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), Irgacure-184 (1-hydroxy cyclohexyl After adding 3 g of phenyl ketone) and stirring, an adhesive composition was prepared.
코팅coating
폴리에틸렌 필름(두께 100㎛) 위에 점착제 조성물을 도포하고, 90℃에서 2분 정도 건조시키고 상온에서 3일 정도 숙성시켰다. 점착제층의 두께는 20㎛이었다. The pressure-sensitive adhesive composition was applied on a polyethylene film (thickness of 100 μm), dried at 90° C. for about 2 minutes, and aged at room temperature for about 3 days. The thickness of the pressure-sensitive adhesive layer was 20 µm.
비교예 1Comparative Example 1
점착제 조성물에 20g의 트리메틸올프로판 트리아크릴레이트(TMPTA)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1, except that 20 g of trimethylolpropane triacrylate (TMPTA) was used in the pressure-sensitive adhesive composition.
비교예 2Comparative Example 2
점착제 조성물에 120g의 트리메틸올프로판 트리아크릴레이트(TMPTA)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1, except that 120 g of trimethylolpropane triacrylate (TMPTA) was used in the pressure-sensitive adhesive composition.
실시예 2Example 2
점착제 조성물로 8g의 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1 except for using 8 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) as the pressure-sensitive adhesive composition.
실시예 3Example 3
점착제 조성물로 15g의 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1, except that 15 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) was used as the pressure-sensitive adhesive composition.
비교예 3Comparative Example 3
점착제 조성물에서 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴)를 사용하지 않는 것을 제외하고 실시예 1과 동일하게 제조하였다.The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) was not used.
비교예 4Comparative Example 4
점착제 조성물에서 2g의 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1 except for using 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) in the pressure-sensitive adhesive composition.
비교예 5Comparative Example 5
점착제 조성물에서 25g의 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴)를 사용하는 것을 제외하고 실시예 1과 동일하게 제조하였다.It was prepared in the same manner as in Example 1 except for using 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) in the pressure-sensitive adhesive composition.
실시예 4Example 4
점착제 조성물에서 광분해 촉매로 2g의 구리(II) 아세테이트를 추가로 첨가한 것을 제외하고 실시예 1과 동일하게 제조하였다.The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 2 g of copper (II) acetate was additionally added as a photolysis catalyst.
실시예 5Example 5
점착제 조성물에서 광분해 촉매로 4g의 구리(II) 아세테이트를 추가로 첨가한 것을 제외하고 실시예 1과 동일하게 제조하였다.The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 4 g of copper (II) acetate was additionally added as a photolysis catalyst.
비교예 6Comparative Example 6
점착제 조성물에서 광분해 촉매로 12g의 구리(II) 아세테이트를 추가로 첨가한 것을 제외하고 실시예 1과 동일하게 제조하였다.The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 12 g of copper (II) acetate was additionally added as a photolysis catalyst.
실시예 6Example 6
코팅단계에서 폴리에틸렌 필름(두께 100㎛) 위에 점착제 조성물을 도트 형태(도트 크기 10mm, 간격 2mm)로 도포하여 건조하는 것을 제외하고 실시예 1과 동일하게 제조하였다.In the coating step, the pressure-sensitive adhesive composition was applied in a dot form (
실시예 7Example 7
실시예 4의 코팅단계에서 폴리에틸렌 필름(두께 100㎛) 위에 점착제 조성물을 도트 형태(도트 크기 10mm, 간격 2mm)로 도포하여 건조하였다.In the coating step of Example 4, the adhesive composition was applied in a dot form (
비교예 7Comparative Example 7
코팅단계에서 폴리에틸렌 필름(두께 100㎛) 위에 점착제 조성물을 도트 형태(도트 크기 2mm, 간격 10mm)로 도포하여 건조하는 것을 제외하고 실시예 1과 동일하게 제조하였다.In the coating step, the pressure-sensitive adhesive composition was applied in a dot form (dot size 2 mm, spacing 10 mm) on a polyethylene film (thickness 100 μm) and prepared in the same manner as in Example 1 except for drying.
실시예 8Example 8
코팅단계에서 폴리에틸렌 필름(두께 100㎛) 위에 점착제 조성물을 도트 형태(도트 크기 20mm, 간격 1mm)로 도포하여 건조하는 것을 제외하고 실시예 1과 동일하게 제조하였다.In the coating step, the pressure-sensitive adhesive composition was applied in the form of dots (
시험exam
ASTM D3330 방법에 따라 SUS-304 피착제에 폭 200mm, 길이 500mm의 보호필름(실시예 1~비교예 8)을 압착하여 시편을 제조하였다. 자외선 조사전 점착력은 압착 20분 후에 측정하였고, 자외선 조사(365nm) 후 접착력은 압착 20분 후에 180mJ의 자외선을 조사한 후 측정하였다. 점착력은 인장기(MECMESIN, ENGLAND)를 이용하여 300mm/min의 속도로 180°박리강도로(gf/inch)를 측정하였다.According to the ASTM D3330 method, specimens were prepared by compressing a protective film (Examples 1 to Comparative Example 8) having a width of 200 mm and a length of 500 mm on a SUS-304 adherend. The adhesive strength before irradiation with ultraviolet rays was measured after 20 minutes of compression, and the adhesive strength after irradiation with ultraviolet rays (365 nm) was measured after irradiation with ultraviolet rays of 180 mJ after 20 minutes of compression. Adhesion was measured as 180 ° peel strength (gf / inch) at a speed of 300 mm / min using a tensile machine (MECMESIN, ENGLAND).
감소율 = (UV 조사전 접착력- UV 조사후 접착력)/UV 조사전 접착력 ×100Reduction rate = (Adhesive strength before UV irradiation-Adhesive strength after UV irradiation)/Adhesive strength before UV irradiation ×100
표 1과 표 2를 참고하면, 광중합성 모노머가 실시예 1 대비 적게 첨가된 비교예 1은 초기 접착력은 비슷하였으나 자외선 조사후의 접착력이 여전히 높았으며, 광중합성 모노머가 실시예 1 대비 다량 첨가된 비교예 2는 광중합성 모노머로 인해 초기 점착력이 현저히 저하되었다. Referring to Tables 1 and 2, Comparative Example 1, in which less photopolymerizable monomer was added than Example 1, had similar initial adhesive strength, but adhesive strength after UV irradiation was still high, and comparison in which a large amount of photopolymerizable monomer was added compared to Example 1 In Example 2, the initial adhesive strength was remarkably lowered due to the photopolymerizable monomer.
아조계 발포 화합물이 첨가된 실시예 2와 3은 첨가되지 않은 비교예 3에 비해 초기 점착력은 다소 떨어졌으나 자외선 조사후의 접착력이 2배 이상 감소하였다. 또한, 아조계 발포 화합물이 소량(2g) 첨가된 비교예 4는 초기 점착력은 실시예 2와 3에 비해 다소 높고, 실시예 1(4g 첨가)과 거의 비숫하였으나, 자외선 조사후의 접착력은 거의 감소되지 않았다. 아조계 발포 화합물을 소량(2g 이내) 첨가하는 경우에 접착력 저하에 영향을 거의 미치지 못하였다.Examples 2 and 3 to which the azo-based foaming compound was added had slightly lower initial adhesive strength compared to Comparative Example 3 to which the azo-based foaming compound was not added, but the adhesive strength after ultraviolet irradiation was reduced by more than two times. In addition, Comparative Example 4 in which a small amount (2 g) of the azo-based foaming compound was added had slightly higher initial adhesive strength than Examples 2 and 3, and was almost the same as Example 1 (4 g added), but the adhesive strength after UV irradiation was hardly reduced. did not In the case of adding a small amount (within 2 g) of the azo-based foaming compound, there was little effect on the decrease in adhesive strength.
실시예 4는 아조계 화합물 4g과 반응성 촉매 2g을 동시에 첨가하여 제조된 점착제로서, 실시예 5는 아조계 화합물 4g과 반응성 촉매 4g을 동시에 첨가하여 제조된 점착제로서, 비교예 6은 아조계 화합물 4g과 반응성 촉매 12g을 동시에 첨가하여 제조된 점착제로서, 실시예 4와 실시예 5는 앞의 실시예 1에 비해 자외선 조사후의 접착력이 2.5배~4배 정도 크게 감소하였다. 하지만, 반응성 촉매가 과량 첨가된 비교예 6은 초기 접착력이 현저히 감소하였다.Example 4 is a pressure-sensitive adhesive prepared by simultaneously adding 4 g of an azo-based compound and 2 g of a reactive catalyst, Example 5 is a pressure-sensitive adhesive prepared by simultaneously adding 4 g of an azo-based compound and 4 g of a reactive catalyst, and Comparative Example 6 is a pressure-sensitive adhesive prepared by simultaneously adding 4 g of an azo-based compound and 4 g of a reactive catalyst. As a pressure-sensitive adhesive prepared by simultaneously adding 12 g of a reactive catalyst, Examples 4 and 5 exhibited a 2.5- to 4-fold decrease in adhesive strength after UV irradiation compared to Example 1. However, in Comparative Example 6 in which an excessive amount of the reactive catalyst was added, the initial adhesive force was significantly reduced.
실시예 6 내지 8은 점착제층에 공극을 형성한 경우로서 초기 접착력이 감소하였으나 자외선 조사후의 접착력이 4배~10배 정도 크게 감소하였다. 특히, 실시예 7(반응성 촉매 사용과 공극 형성)은 자외선 조사후의 접착력이 실시예 1 대비 10배 크게 감소하였다. 비교예 7은 점착제층의 비율이 적어 초기 접착력이 크게 감소하였다. In Examples 6 to 8, when pores were formed in the pressure-sensitive adhesive layer, the initial adhesive strength was reduced, but the adhesive strength after ultraviolet irradiation was greatly reduced by about 4 to 10 times. In particular, in Example 7 (use of a reactive catalyst and formation of pores), the adhesive strength after UV irradiation was greatly reduced by 10 times compared to Example 1. In Comparative Example 7, the initial adhesive strength was greatly reduced due to the small ratio of the pressure-sensitive adhesive layer.
지금까지 본 발명의 구체적인 실시예들을 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본질적인 특성에 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.So far, we looked at specific embodiments of the present invention. Those skilled in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from its essential characteristics. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.
Claims (5)
상기 혼합용액을 열중합하는 아크릴 공중합체 제조단계 ;
제조된 상기 아크릴 공중합체 용액에 광중합성 모노머, 광개시제 및 아조계 화합물을 혼합하는 점착제 조성물 제조단계 ;
상기 점착제 조성물을 기재필름 상에 코팅하여 건조시키는 점착제층 형성단계를 포함하고,
상기 점착제층 형성단계는 상기 점착제 조성물을 홀이 형성된 드럼을 사용하여 도트(dot) 형태로 인쇄하는 단계 및 이를 건조하는 단계를 포함하고,
상기 아크릴 공중합체 제조단계는
아크릴 단량체 100중량부 대비 비닐계 단량체 5~10중량부, 열경화성 개시제 0.1~2중량부를 용매에 넣어 혼합한 후 열중합으로 제조하고,
상기 아크릴 단량체는 메틸아크릴레이트, 에틸아크릴레이트, 부틸아크릴레이트, 2-에틸부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 헥실아크릴레이트이고,
상기 비닐계 단량체는 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-하이드록시헥실(메트)아크릴레이트, 2-하이드록시에틸렌글리콜(메트)아크릴레이트 또는 2-하이드록시프로필렌글리콜(메트)아크릴레이트이고,
상기 광중합성 모노머는 트리메틸올프로판 트리아크릴레이트(TMPTA), 폴리에틸렌글리콜 디아크릴레이트, 에틸렌옥사이드 부가형 트리메틸올프로판트리아크릴레이트, 에톡시 부가형트리에틸올프로판 트리아크릴레이트, 펜타에리스리톨 테트라아크릴레이트(PETA), 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트 및 이들의 혼합물로 이루어지는 군으로부터 선택되는 1종 이상이고,
상기 아조계 화합물이 2,2-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 2,2-아조비스(2,4-디메틸발레로니트릴), 2,2-아조비스이소부티로니트릴, 디메틸 2,2-아조비스이소부티레이트, 2,2-아조비스(2-메틸부티로니트릴), 1,1-아조비스(1-시클로헥산카보니트릴) 및 2,2-아조비스(2,4,4-트리메틸펜탄)으로 이루어진 군으로부터 선택되는 1종 이상이고,
상기 점착제 조성물 제조단계는 상기 아조계 화합물의 반응을 촉진하는 광분해 촉매를 추가로 포함하고, 상기 광분해 촉매는 코발트(II) 아세테이트 또는 구리(II) 아세테이트인 것을 특징으로 하는 자외선 경화형 보호 필름의 제조방법. mixing an acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a vinyl monomer, and a thermosetting initiator in a solvent;
Preparing an acrylic copolymer by thermally polymerizing the mixed solution;
A pressure-sensitive adhesive composition preparation step of mixing a photopolymerizable monomer, a photoinitiator, and an azo-based compound with the prepared acrylic copolymer solution;
A pressure-sensitive adhesive layer forming step of coating the pressure-sensitive adhesive composition on a base film and drying it,
The step of forming the pressure-sensitive adhesive layer includes printing the pressure-sensitive adhesive composition in a dot form using a drum having holes and drying the pressure-sensitive adhesive composition,
The step of preparing the acrylic copolymer is
5 to 10 parts by weight of a vinyl monomer and 0.1 to 2 parts by weight of a thermosetting initiator are mixed in a solvent based on 100 parts by weight of an acrylic monomer, and then prepared by thermal polymerization,
The acrylic monomer is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate or hexyl acrylate,
The vinyl-based monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2 -Hydroxyethylene glycol (meth)acrylate or 2-hydroxypropylene glycol (meth)acrylate,
The photopolymerizable monomer is trimethylolpropane triacrylate (TMPTA), polyethylene glycol diacrylate, ethylene oxide addition type trimethylolpropane triacrylate, ethoxy addition type triethylolpropane triacrylate, pentaerythritol tetraacrylate (PETA) , 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and at least one selected from the group consisting of mixtures thereof,
The azo-based compound is 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis Isobutyronitrile, dimethyl 2,2-azobisisobutyrate, 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(1-cyclohexanecarbonitrile) and 2,2-azo At least one selected from the group consisting of bis (2,4,4-trimethylpentane),
The step of preparing the pressure-sensitive adhesive composition further includes a photolysis catalyst that promotes the reaction of the azo-based compound, and the photolysis catalyst is a method for producing an ultraviolet curable protective film, characterized in that cobalt (II) acetate or copper (II) acetate. .
상기 아크릴 단량체 100중량부 대비, 광중합성 모노머 10~20중량부, 광개시제 1 ~ 5중량부 및 아조계 화합물 1~10중량부를 포함하는 것을 특징으로 하는 자외선 경화형 보호 필름의 제조방법. The method of claim 1, wherein the pressure-sensitive adhesive composition manufacturing step
A method for producing an ultraviolet curable protective film comprising 10 to 20 parts by weight of a photopolymerizable monomer, 1 to 5 parts by weight of a photoinitiator, and 1 to 10 parts by weight of an azo compound, relative to 100 parts by weight of the acrylic monomer.
상기 보호필름은 이형지 제거 후 피보호 대상물에 부착되고,
상기 피보호 대상물의 소정 작업이 완료된 후 상기 보호필름에 자외선이 조사되면,
상기 보호필름은 광중합성 모노머의 광중합과 상기 아조계 화합물의 발포로 인해 자외선 조사 전에 비해 접착력이 저하되거나,
상기 보호필름은 상기 도트와 도트 사이에 공극이 형성되어 탈착력이 저하되는 것을 특징으로 하는 자외선 경화형 보호 필름.
An ultraviolet curable protective film prepared by the manufacturing method of any one of claims 1, 2 and 4,
The protective film is attached to the object to be protected after removing the release paper,
When the protective film is irradiated with ultraviolet rays after the predetermined operation of the object to be protected is completed,
The protective film has a lower adhesive strength than before UV irradiation due to photopolymerization of the photopolymerizable monomer and foaming of the azo-based compound,
The protective film is an ultraviolet curable protective film, characterized in that a gap is formed between the dots and the detachability is reduced.
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| KR20050004893A (en) * | 2002-05-31 | 2005-01-12 | 더 프록터 앤드 갬블 캄파니 | Embossing and adhesive printing process |
| KR20080073883A (en) * | 2007-02-07 | 2008-08-12 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for the polarizing film |
| JP2011522063A (en) * | 2008-04-21 | 2011-07-28 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| KR20150003011A (en) * | 2013-06-28 | 2015-01-08 | 동우 화인켐 주식회사 | Photocurable adhesive composition for polarizing plate |
| KR102099538B1 (en) * | 2019-10-23 | 2020-04-09 | 김진우 | Dual curing type adhesive tape |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002522192A (en) * | 1998-08-03 | 2002-07-23 | ザ、プロクター、エンド、ギャンブル、カンパニー | Improved adhesive printing process for disposable absorbers |
| KR20050004893A (en) * | 2002-05-31 | 2005-01-12 | 더 프록터 앤드 갬블 캄파니 | Embossing and adhesive printing process |
| KR20080073883A (en) * | 2007-02-07 | 2008-08-12 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for the polarizing film |
| JP2011522063A (en) * | 2008-04-21 | 2011-07-28 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
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| KR102099538B1 (en) * | 2019-10-23 | 2020-04-09 | 김진우 | Dual curing type adhesive tape |
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