JP6111781B2 - Adhesive composition and adhesive tape - Google Patents
Adhesive composition and adhesive tape Download PDFInfo
- Publication number
- JP6111781B2 JP6111781B2 JP2013066367A JP2013066367A JP6111781B2 JP 6111781 B2 JP6111781 B2 JP 6111781B2 JP 2013066367 A JP2013066367 A JP 2013066367A JP 2013066367 A JP2013066367 A JP 2013066367A JP 6111781 B2 JP6111781 B2 JP 6111781B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- adhesive composition
- adhesive tape
- mass
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 77
- 230000001070 adhesive effect Effects 0.000 title claims description 40
- 239000000853 adhesive Substances 0.000 title claims description 35
- 239000002390 adhesive tape Substances 0.000 title claims description 22
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 129
- 239000011256 inorganic filler Substances 0.000 claims description 48
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 41
- 239000002270 dispersing agent Substances 0.000 claims description 39
- 229920006243 acrylic copolymer Polymers 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 239000003063 flame retardant Substances 0.000 claims description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 n-octyl Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
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- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
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- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、良好な熱伝導性や難燃性を有し、接着性に優れた粘着剤組成物及び粘着テープに関し、電子部品、ＯＡ機器部品、家電部品等の各種分野での部材の固定用途、特に発熱性のＬＥＤの固定用途に有用である粘着剤組成物及び粘着テープに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape having good thermal conductivity and flame retardancy, and excellent adhesion, and for fixing members in various fields such as electronic parts, OA equipment parts, home appliance parts, etc. In particular, the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that are useful for fixing heat-generating LEDs.
近年、エレクトロニクス技術の格段なる進歩により電気、電子、ＯＡ機器の高集積化・高性能化が進み、内部の高温化や蓄熱による不具合が生じやすくなっており、内部部品の固定に使用する接着部材にも高温化や蓄熱を防止するための高い熱伝導性が求められている。また、仮に過剰な高温化や蓄熱が生じた際にも発火危険性を防止するため、接着部材には高い難燃性も求められている。近年の電子機器やＯＡ機器は軽薄短小化が進んでおり、限られた放熱空間にて放熱が必要であり、特に、画像表示のバックライトに使用されるＬＥＤ光源は発熱しやすく、また、画像表示部の輝度を確保するために実装密度を上げるとさらに発熱量が増大することから、高い放熱性や難燃性が求められている。 In recent years, remarkable progress in electronics technology has led to higher integration and higher performance of electrical, electronic, and OA equipment, which has been prone to problems caused by internal high temperatures and heat storage. Adhesive members used for fixing internal components In addition, high thermal conductivity is required to prevent high temperature and heat storage. Moreover, in order to prevent the risk of ignition even when excessive temperature increase or heat storage occurs, the adhesive member is also required to have high flame retardancy. In recent years, electronic devices and OA devices are becoming lighter, thinner, and smaller, and it is necessary to dissipate heat in a limited heat-dissipating space. In particular, LED light sources used for image display backlights tend to generate heat. When the mounting density is increased in order to ensure the luminance of the display portion, the amount of heat generation is further increased. Therefore, high heat dissipation and flame retardancy are required.
熱伝導性や難燃性を有する粘着性の組成物としては、例えば、アクリル系ポリマーに難燃剤及び熱伝導性フィラーを含有する熱伝導性難燃性感圧接着剤（特許文献１参照）や、
（メタ）アクリレート系ポリマーと金属水酸化物とを有し、（メタ）アクリレート系ポリマーのトルエン不溶分の割合とトルエン可溶分の分子量とを特定の範囲とし、（メタ）アクリレート系ポリマー１００質量部に対する金属水酸化物の配合割合が８０〜１６０質量部である感圧接着剤組成物が開示されている（特許文献２参照）。
As an adhesive composition having thermal conductivity and flame retardancy, for example, a thermally conductive flame-retardant pressure-sensitive adhesive (see Patent Document 1) containing a flame retardant and a thermally conductive filler in an acrylic polymer,
It has a (meth) acrylate polymer and a metal hydroxide, has a specific range of the toluene-insoluble fraction of the (meth) acrylate polymer and the molecular weight of the toluene-soluble component, and 100 mass of the (meth) acrylate polymer. A pressure-sensitive adhesive composition in which the blending ratio of the metal hydroxide to 80 parts is 80 to 160 parts by mass is disclosed (see Patent Document 2).
これら感圧接着材は、難燃性及び熱伝導性を有するが、軽薄短小化が進んだ電子機器やＯＡ機器等への適用に際し、難燃性や熱伝導性を向上させるため、難燃剤や熱伝導性フィラーの添加量を増加すると、無機フィラーの分散性が低下する問題があった。 These pressure-sensitive adhesives have flame retardancy and thermal conductivity. However, in order to improve flame retardancy and thermal conductivity when applied to electronic devices and OA devices that are becoming lighter and thinner, flame retardants and When the addition amount of the heat conductive filler is increased, there is a problem that the dispersibility of the inorganic filler is lowered.
このような問題に対し、粘着剤組成物中の無機フィラーの分散性の向上を目的に、リン酸系分散剤や、各種塩系の分散剤等の分散剤の添加が行われている（特許文献３〜５参照）。しかし、粘着剤に高い難燃性等を付与するためにエポキシ系架橋剤を使用した場合には、リン酸系分散剤等の各種酸系の分散剤を添加すると架橋阻害が生じる問題があった。また、塩系の分散剤では多量の無機フィラーを分散させると経時でケーキングを生じる問題があった。 In order to improve the dispersibility of the inorganic filler in the pressure-sensitive adhesive composition, a dispersing agent such as a phosphoric acid-based dispersant or various salt-based dispersants has been added (patents). Reference 3-5). However, when an epoxy-based cross-linking agent is used to impart high flame retardancy to the pressure-sensitive adhesive, there is a problem that cross-linking inhibition occurs when various acid-based dispersants such as a phosphoric acid-based dispersant are added. . Further, the salt-based dispersant has a problem that caking occurs with time when a large amount of inorganic filler is dispersed.
本発明が解決ようとする課題は、良好な熱伝導性や難燃性を実現するために無機フィラーを多く添加しても、無機フィラーの分散性が良好で、かつケーキングを生じにくい粘着剤組成物を提供することにある。 The problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition that has good dispersibility of the inorganic filler and hardly causes caking even if a large amount of inorganic filler is added to achieve good thermal conductivity and flame retardancy. To provide things.
本発明においては、（メタ）アクリレートモノマーを主たるモノマー成分とするアクリル系共重合体、無機フィラー及びエポキシ系架橋剤を含有し、無機フィラーの含有量がアクリル共重合体１００質量部に対して２００質量部以上であり、分散剤としてアミン系分散剤を含有する粘着剤組成物により、多量の無機フィラーを添加した場合にも無機フィラーの分散性が良好で、かつケーキングを抑制でき、良好な難燃性や熱伝導性、さらには好適な接着性を有する粘着剤を実現できる。 In the present invention, an acrylic copolymer containing an (meth) acrylate monomer as a main monomer component, an inorganic filler, and an epoxy crosslinking agent are contained, and the content of the inorganic filler is 200 with respect to 100 parts by mass of the acrylic copolymer. Even when a large amount of inorganic filler is added by the pressure-sensitive adhesive composition containing an amine dispersant as a dispersant, the dispersibility of the inorganic filler is good and caking can be suppressed. A pressure-sensitive adhesive having flammability, thermal conductivity, and suitable adhesiveness can be realized.
本発明の粘着剤組成物は、良好な難燃性や熱伝導性を実現するために無機フィラーを多く添加しても、良好に無機フィラーを分散でき、かつケーキングを抑制できることから保存安定性に優れる。また、架橋阻害を生じることなく良好な接着性を有し、かつ多くの無機フィラーを含有できることから、優れた難燃性や熱伝導性を実現できる。このため、本発明の粘着剤組成物は、部品固定に高い信頼性が求められ、かつ、近年の軽薄短小化が進む各種の電子機器やＯＡ機器等の電子部品の固定に好適に適用できる。なかでも、発熱量が大きく、画像表示部の輝度を確保するために高い実装密度が求められる画像表示のバックライト等に使用されるＬＥＤ光源の固定に特に好適に使用できる。 The pressure-sensitive adhesive composition of the present invention has excellent storage stability because it can disperse the inorganic filler satisfactorily and suppress caking even when a large amount of inorganic filler is added to achieve good flame retardancy and thermal conductivity. Excellent. Moreover, since it has favorable adhesiveness without causing crosslinking inhibition and can contain many inorganic fillers, excellent flame retardancy and thermal conductivity can be realized. For this reason, the pressure-sensitive adhesive composition of the present invention can be suitably applied to fixing electronic components such as various electronic devices and OA devices that are required to have high reliability for fixing components and that are becoming lighter and thinner in recent years. Among these, the amount of heat generation is large, and it can be particularly suitably used for fixing an LED light source used for an image display backlight or the like that requires a high mounting density in order to ensure the luminance of the image display unit.
［粘着剤組成物］
本発明の粘着剤組成物は、（メタ）アクリレートモノマーを主たるモノマー成分とするアクリル系共重合体、無機フィラー及びエポキシ系架橋剤を含有する粘着剤組成物であって、前記無機フィラーの含有量が、アクリル系共重合体１００質量部に対して２００質量部以上であり、分散剤としてアミン系分散剤を含有する粘着剤組成物。である。
[Adhesive composition]
The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing an acrylic copolymer having a (meth) acrylate monomer as a main monomer component, an inorganic filler, and an epoxy-based crosslinking agent, and the content of the inorganic filler However, it is 200 mass parts or more with respect to 100 mass parts of acrylic copolymers, and contains the amine-type dispersing agent as a dispersing agent. It is.
（アクリル系共重合体）
本発明に使用するアクリル系共重合体は、（メタ）アクリレートモノマーを主たるモノマー成分とするアクリル系共重合体である。主たるモノマー成分として使用する（メタ）アクリレートとしては、粘着剤に使用する各種（メタ）アクリレートを使用でき、なかでもアルキル基の炭素数１〜１２のアルキル（メタ）アクリレートを好ましく使用できる。炭素数１〜１２のアルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のモノマーがあげられ、これらの１種または２種以上が用いられる。なかでも、アルキル基の炭素数が４〜８のアルキル（メタ）アクリレート、特にｎ−ブチルアクリレート及び２−エチルヘキシルアクリレートはフィラーを添加しても粘着性を確保しやすいため好ましい。
(Acrylic copolymer)
The acrylic copolymer used in the present invention is an acrylic copolymer having a (meth) acrylate monomer as a main monomer component. As the (meth) acrylate used as the main monomer component, various (meth) acrylates used for the pressure-sensitive adhesive can be used, and among them, alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group can be preferably used. Examples of the alkyl (meth) acrylate having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Examples include monomers such as n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and one or more of these are used. It is done. Of these, alkyl (meth) acrylates having 4 to 8 carbon atoms in the alkyl group, particularly n-butyl acrylate and 2-ethylhexyl acrylate, are preferable because they can easily secure adhesiveness even when a filler is added.
炭素数１〜１２のアルキル（メタ）アクリレートの含有量は、アクリル系共重合体を構成するモノマー成分中の５０質量％以上とすることが好ましく、６０〜９８質量％であることが好ましく、８０質量％〜９８質量％以上であることが更に好ましい。 The content of the alkyl (meth) acrylate having 1 to 12 carbon atoms is preferably 50% by mass or more, preferably 60 to 98% by mass in the monomer component constituting the acrylic copolymer, 80 It is still more preferable that it is mass%-98 mass% or more.
また、本発明の粘着剤組成物においては、上記主たる（メタ）アクリレートモノマーに、架橋剤と架橋反応するビニルモノマーとして炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーを併用することが好ましい。当該炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーを使用することでアクリル系共重合体に無機フィラーを多量に含有しても凝集性と流動性とを特に好適に兼備できる。炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは、側鎖が長いため架橋点の流動性に優れる。また、炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは、ガラス転移温度が低いため、粘着剤層の損失正接のピークを示す温度が低くなり、流動性に優れる粘着剤組成物を実現できる。さらに、炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは立体障害が少ないため末端のカルボキシ基と架橋剤が反応しやすく粘着剤組成物の凝集力を得ることができる。このように、当該（メタ）アクリレートモノマーを使用することで、樹脂の凝集力を低下させずに粘着剤の凝集性と流動性を両立でき、得られる粘着剤組成物は多量のフィラーを含有しても特に優れた粘着物性を示す。 In the pressure-sensitive adhesive composition of the present invention, the main (meth) acrylate monomer is a vinyl monomer that undergoes a crosslinking reaction with a crosslinking agent, and a carboxy group is terminated at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms. It is preferable to use together the (meth) acrylate monomer which has. By using a (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms, the acrylic copolymer can be cohesive even if it contains a large amount of an inorganic filler. The fluidity can be particularly suitably combined. A (meth) acrylate monomer having a carboxy group at the end of a molecular chain via a saturated hydrocarbon group having 2 or more carbon atoms is excellent in fluidity at a crosslinking point because of a long side chain. In addition, since the (meth) acrylate monomer having a carboxy group at the molecular chain terminal via a saturated hydrocarbon group having 2 or more carbon atoms has a low glass transition temperature, the temperature at which the loss tangent peak of the pressure-sensitive adhesive layer is low is low. Thus, an adhesive composition having excellent fluidity can be realized. Furthermore, since the (meth) acrylate monomer having a carboxy group at the molecular chain end via a saturated hydrocarbon group having 2 or more carbon atoms has little steric hindrance, the terminal carboxy group and the crosslinking agent can easily react with each other. Cohesive force can be obtained. Thus, by using the (meth) acrylate monomer, it is possible to achieve both cohesiveness and fluidity of the adhesive without reducing the cohesive strength of the resin, and the resulting adhesive composition contains a large amount of filler. However, it exhibits particularly excellent adhesive properties.
炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーとしては、例えば、下式（１）にて表わされる（メタ）アクリレートモノマーを例示できる。 Examples of the (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms include a (meth) acrylate monomer represented by the following formula (1).
なお、上記ジカルボン酸残基とは、分子鎖末端にジカルボン酸の一方のカルボキシ基が結合した構造におけるジカルボン酸の残基を表し、例えば、ＨＯＯＣ−Ｒ−ＣＯＯＨとして表わされるジカルボン酸により形成されるジカルボン酸残基は−ＯＯＣ−Ｒ−ＣＯＯＨである。当該ジカルボン酸残基を構成するジカルボン酸としては、上記Ｒが直接結合したジカルボン酸や、上記Ｒとして二価の脂肪族炭化水素基や芳香族炭化水素基を有するジカルボン酸を適宜使用でき、なかでも脂肪族炭化水素基、特に鎖状脂肪族炭化水素基を有するジカルボン酸は立体障害が生じにくいため好ましい。好適なジカルボン酸としては、具体的には、シュウ酸、マロン酸、コハク酸、マレイン酸、フマル酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸等を例示できる。 In addition, the said dicarboxylic acid residue represents the residue of the dicarboxylic acid in the structure which one carboxy group of dicarboxylic acid couple | bonded with the molecular chain terminal, For example, it forms with the dicarboxylic acid represented as HOOC-R-COOH. The dicarboxylic acid residue is -OOC-R-COOH. As the dicarboxylic acid constituting the dicarboxylic acid residue, a dicarboxylic acid in which R is directly bonded, or a dicarboxylic acid having a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group as R can be appropriately used. However, dicarboxylic acids having an aliphatic hydrocarbon group, particularly a chain aliphatic hydrocarbon group, are preferred because steric hindrance is unlikely to occur. Specific examples of suitable dicarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. It can be illustrated.
上記式（１）で表わされる（メタ）アクリレートのなかでも、Ｒ２が炭素数２〜１８のアルキレン基であることが好ましく、炭素数が２〜５のアルキレン基であることが特に好ましい。また、Ｘ１がカルボキシ基であることが好ましい。具体的には、例えば、β−カルボキシアルキル（メタ）アクリレート、エチレンオキサイド（ＥＯ）変性コハク酸（メタ）アクリレート、プロピレンオキサイド（ＰＯ）変性コハク酸（メタ）アクリレート等が例示できる。これらのなかでも、β−カルボキシエチルアクリレートを特に好ましく使用できる。 Among the (meth) acrylates represented by the above formula (1), R 2 is preferably an alkylene group having 2 to 18 carbon atoms, and particularly preferably an alkylene group having 2 to 5 carbon atoms. X 1 is preferably a carboxy group. Specifically, for example, β-carboxyalkyl (meth) acrylate, ethylene oxide (EO) modified succinic acid (meth) acrylate, propylene oxide (PO) modified succinic acid (meth) acrylate and the like can be exemplified. Among these, β-carboxyethyl acrylate can be particularly preferably used.
炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーの含有量は、アクリル系共重合体を構成するモノマー成分中の０．５〜１０質量％であることが好ましく、１〜５質量％であることがより好ましい。炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーの含有量を当該範囲とすることで、架橋点を好適に形成しやすくなり、粘着剤の凝集力や初期接着性を向上させやすくなる。 The content of the (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms is 0.5 to 10% by mass in the monomer component constituting the acrylic copolymer. It is preferable that it is 1-5 mass%. By setting the content of the (meth) acrylate monomer having a carboxy group at the end of the molecular chain through a saturated hydrocarbon group having 2 or more carbon atoms within the above range, a crosslinking point can be easily formed, It becomes easy to improve cohesion force and initial adhesiveness.
アクリル系共重合体を構成するモノマー成分としては、上記以外のモノマー成分として、各種ビニルモノマーを使用できる。このようなビニルモノマーとしては、カルボキシ基含有モノマーを好ましく使用でき、当該カルボキシ基含有ビニルモノマーとしては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、無水マレイン酸、フタル酸、無水フタル酸、クロトン酸等の１種又は２種以上を使用できる。なかでもアクリル酸、メタクリル酸は、アクリル系共重合体の凝集性を好適に調整しやすいため好ましく使用できる。 As the monomer component constituting the acrylic copolymer, various vinyl monomers can be used as monomer components other than those described above. As such a vinyl monomer, a carboxy group-containing monomer can be preferably used. Examples of the carboxy group-containing vinyl monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, and phthalic anhydride. 1 type, or 2 or more types, such as crotonic acid, can be used. Of these, acrylic acid and methacrylic acid can be preferably used because they easily adjust the cohesiveness of the acrylic copolymer.
当該カルボキシ基含有ビニルモノマーの含有量は、アクリル系共重合体を構成するモノマー成分中の１０質量％以下であることが好ましく、０．５〜１０質量％であることがさらに好ましく、１〜５質量％であることがより好ましい。当該範囲で含有することにより、粘着剤の凝集力や保持力、接着性を、向上させやすい。 The content of the carboxy group-containing vinyl monomer is preferably 10% by mass or less, more preferably 0.5 to 10% by mass, and more preferably 1 to 5% in the monomer component constituting the acrylic copolymer. More preferably, it is mass%. By containing in the said range, it is easy to improve the cohesive force, holding force, and adhesiveness of an adhesive.
また、その他のビニルモノマーとして、酢酸ビニル、２−アクリルアミド−２−メチルプロパンスルフォン酸等のスルホン酸基含有モノマー、炭素数１〜３の（メタ）アクリレート、炭素数１３以上の（メタ）アクリレート、イソボルニル（メタ）アクリレート、スチレン等、公知のビニルモノマーを使用してもよい。 Other vinyl monomers include vinyl acetate, sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylates having 1 to 3 carbon atoms, (meth) acrylates having 13 or more carbon atoms, Known vinyl monomers such as isobornyl (meth) acrylate and styrene may be used.
その他のビニルモノマーを使用する場合の含有量は、アクリル系共重合体を構成するモノマー成分中の１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。当該範囲で含有することにより、粘着剤の凝集力や保持力、接着性を好適な範囲に調整しやすい。 The content in the case of using other vinyl monomers is preferably 10% by mass or less, more preferably 5% by mass or less, in the monomer component constituting the acrylic copolymer. By containing in the said range, it is easy to adjust the cohesive force, holding force, and adhesiveness of an adhesive to a suitable range.
上記アクリル系共重合は、溶液重合法、塊状重合法などの公知の重合方法により共重合させることにより得ることができる。重合開始方法も過酸化ベンゾイルや過酸化ラウリロイルなどの過酸化物系、アゾビスイソブチルニトリルなどのアゾ系の熱重合開始剤を用いた熱による開始方法や、アセトフェノン系、ベンゾインエーテル系、ベンジルケタール系、アシルフォスフィンオキシド系、ベンゾイン系、ベンゾフェノン系の光重合開始剤を用いた紫外線照射による開始方法や、電子線照射による方法を任意に選択できる。 The acrylic copolymer can be obtained by copolymerization by a known polymerization method such as a solution polymerization method or a bulk polymerization method. Polymerization is initiated by peroxides such as benzoyl peroxide and lauryl peroxide, thermal initiation methods using azo-based thermal polymerization initiators such as azobisisobutylnitrile, acetophenone, benzoin ether, benzyl ketal In addition, an initiation method by ultraviolet irradiation using an acylphosphine oxide-based, benzoin-based or benzophenone-based photopolymerization initiator, or a method by electron beam irradiation can be arbitrarily selected.
上記範囲内で重合したアクリル系共重合体は、ゲルパーミエーションクロマトグラフィのポリスチレン換算による重量平均分子量が３０万〜８０万、より好ましくは４０万〜７０万である。重量平均分子量が３０万以上とすることで粘着剤の凝集力を確保しやすくなり、高温下での接着性を向上させやすい。また重量平均分子量が８０万以下とすることで、熱伝導性フィラーの分散性や、粘着剤の塗工性、初期接着性を向上させやすい。 The acrylic copolymer polymerized within the above range has a weight average molecular weight in terms of polystyrene of gel permeation chromatography of 300,000 to 800,000, more preferably 400,000 to 700,000. When the weight average molecular weight is 300,000 or more, the cohesive force of the pressure-sensitive adhesive is easily secured, and the adhesiveness at high temperature is easily improved. Moreover, it is easy to improve the dispersibility of a heat conductive filler, the applicability | paintability of an adhesive, and initial stage adhesiveness because a weight average molecular weight shall be 800,000 or less.
（無機フィラー）
本発明に使用する無機フィラーは、熱伝導性や難燃性を有する無機フィラーを使用でき、例えば、金属水酸化物、金属酸化物、金属、セラミックス等を使用できる。具体的には、熱伝導性のフィラーとして、例えば、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化鉄、炭化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、窒化ケイ素、ホウ素化チタン、カーボン、ニッケル、銅、アルミニウム、チタン、金、銀等が挙げられる。また、難燃性のフィラーとしては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、塩基性炭酸マグネシウム、ドロマイト、ハイドロタルサイト、水酸化カルシウム、水酸化バリウム、酸化スズの水和物、硼砂などの無機金属化合物の水和物、ホウ酸亜鉛、メタホウ酸亜鉛、メタホウ酸バリウム、炭酸亜鉛、炭酸マグネシウム−カルシウム、炭酸カルシウム、炭酸バリウム、酸化マグネシウム、酸化モリブデン、酸化ジルコニウム、酸化スズ、酸化アンチモン、赤リン等が挙げられる。これら無機フィラーは、アクリル系共重合体への分散性向上のため、シランカップリング処理、ステアリン酸処理などの表面処理を施してもよい。
(Inorganic filler)
The inorganic filler used for this invention can use the inorganic filler which has heat conductivity and a flame retardance, for example, can use a metal hydroxide, a metal oxide, a metal, ceramics, etc. Specifically, as the thermally conductive filler, for example, aluminum hydroxide, magnesium hydroxide, aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, iron oxide, silicon carbide, boron nitride, nitriding Examples thereof include aluminum, titanium nitride, silicon nitride, titanium boride, carbon, nickel, copper, aluminum, titanium, gold, and silver. Examples of the flame retardant filler include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide hydrate, Hydrate of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate-calcium carbonate, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, oxidation Examples include antimony and red phosphorus. These inorganic fillers may be subjected to surface treatment such as silane coupling treatment or stearic acid treatment in order to improve dispersibility in the acrylic copolymer.
これら無機フィラーは、必要に応じて適宜選択して使用すればよいが、これらのなかでも、熱伝導性及び難燃性が必要な用途においては、熱伝導性及び難燃性を有する熱伝導難燃性フィラーを使用することが好ましい。特に、ＬＥＤ固定用途においては、熱伝導難燃性フィラーとして、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物を使用することが特に好ましい。これらの金属水酸化物は熱伝導性と難燃性を付与することができる。特に金属水酸化物の中で水酸化アルミニウムは、２５０℃程度から熱分解反応が起こり、樹脂が著しく溶融する前に難燃効果を発揮するため好ましい。 These inorganic fillers may be appropriately selected and used as necessary, but among these, in applications that require thermal conductivity and flame retardancy, thermal conductivity and flame retardance are difficult. It is preferable to use a flammable filler. In particular, in LED fixing applications, it is particularly preferable to use a metal hydroxide such as aluminum hydroxide or magnesium hydroxide as the heat conductive flame retardant filler. These metal hydroxides can impart thermal conductivity and flame retardancy. Among the metal hydroxides, aluminum hydroxide is particularly preferable because a thermal decomposition reaction takes place from about 250 ° C. and exhibits a flame retardant effect before the resin is remarkably melted.
無機フィラーの形状は、規則的な形状又は不規則な形状のいずれであってもよく、例えば、多角形状、立方体状、楕円状、球状、針状、平板状、鱗片状又はこれらを組み合わせた形状等が挙げられ、これらが凝集したフィラーであってもよい。無機フィラーの大きさは、最大となる幅や長さの平均、例えば粒子状の場合にはその平均粒径が、０．５〜５０μｍであることが好ましい。より好ましくは１〜３０μｍである。なお、フィラーの大きさ、形状は、得られる粘着テープの厚さにより適宜選択される。粘着テープの厚さよりも無機フィラーの最大の幅や長さが小さい方が望ましい。 The shape of the inorganic filler may be either a regular shape or an irregular shape, such as a polygonal shape, a cubic shape, an elliptical shape, a spherical shape, a needle shape, a flat plate shape, a scale shape, or a combination thereof. Etc., and these may be agglomerated fillers. As for the size of the inorganic filler, it is preferable that the average of the maximum width and length, for example, in the case of particles, the average particle size is 0.5 to 50 μm. More preferably, it is 1-30 micrometers. In addition, the magnitude | size and shape of a filler are suitably selected by the thickness of the adhesive tape obtained. It is desirable that the maximum width and length of the inorganic filler be smaller than the thickness of the adhesive tape.
粘着剤組成物への無機フィラーの添加量としては、良好な熱伝導性や難燃性を実現するために、アクリル系共重合体１００質量部に対し２００質量部以上、好ましくは２００質量部〜２８０質量部、より好ましくは２３０〜２５０質量部である。本発明の粘着剤組成物は、当該多量の無機フィラーを含有しても好適な接着性を実現できる。 The amount of the inorganic filler added to the pressure-sensitive adhesive composition is 200 parts by mass or more, preferably 200 parts by mass to 100 parts by mass of the acrylic copolymer in order to realize good thermal conductivity and flame retardancy. It is 280 mass parts, More preferably, it is 230-250 mass parts. Even if the pressure-sensitive adhesive composition of the present invention contains the large amount of the inorganic filler, suitable adhesiveness can be realized.
（粘着付与樹脂）
本発明の熱伝導性粘着剤には粘着物性を向上する目的で粘着付与樹脂を使用してもよい。粘着付与樹脂としては公知の脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系石油樹脂などの石油樹脂、ロジン樹脂、ロジンエステル樹脂、不均化ロジン樹脂、重合ロジン樹脂、重合ロジンエステル樹脂、ロジンフェノールなどのロジン系樹脂、テルペン樹脂、テルペンフェノール樹脂などが使用できる。また粘着付与樹脂は２種類以上の樹脂を併用することができる。
(Tackifying resin)
A tackifier resin may be used in the heat conductive adhesive of the present invention for the purpose of improving adhesive properties. As tackifying resins, known aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, etc., rosin resins, rosin ester resins, disproportionated rosin resins, polymerized rosin resins, polymerized rosin esters Resins, rosin resins such as rosin phenol, terpene resins, terpene phenol resins and the like can be used. Further, two or more kinds of tackifying resins can be used in combination.
粘着付与樹脂の添加量としては、アクリル系共重合体１００質量部に対し２０質量部以下が好ましい。より好ましくは１０質量部以下である。当該範囲とすることで、良好な粘着付与効果や初期接着性を得られやすくなる。また、特に高い難燃性、例えばＵＬ９４Ｖ−０やＶＴＭ−０等の高い難燃性を要求される用途については、粘着付与樹脂を使用しないことも好ましい。 As addition amount of tackifying resin, 20 mass parts or less are preferable with respect to 100 mass parts of acrylic copolymers. More preferably, it is 10 parts by mass or less. By setting it as the said range, it will become easy to acquire a favorable tackifying effect and initial stage adhesiveness. Moreover, it is also preferable not to use a tackifying resin for applications that require particularly high flame retardancy, for example, high flame retardancy such as UL94V-0 and VTM-0.
また、粘着付与樹脂は、引火点が高い粘着付与樹脂を使用することが好ましく、引火点が２００度以上の樹脂を使用することが特に好ましい。引火点が２００度以上の粘着付与樹脂を使用すると、難燃性フィラーが燃焼時に熱分解して生じる難燃効果を特に効率的に発揮しやすくなる。 Moreover, it is preferable to use tackifying resin with a high flash point, and it is especially preferable to use resin with a flash point of 200 degree | times or more as tackifying resin. When a tackifying resin having a flash point of 200 degrees or more is used, it becomes easy to particularly effectively exhibit a flame retardant effect produced by thermal decomposition of the flame retardant filler during combustion.
（架橋剤）
本発明の粘着剤組成物にはエポキシ系架橋剤を使用することで、凝集力及び耐熱性を向上できる。エポキシ系架橋剤としては、１．３−ビス（Ｎ，Ｎ―グリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製テトラッドＣ）、１．３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）ベンゼン（三菱ガス化学社製テトラッドＸ）など公知のエポキシ系架橋剤を使用できる。
(Crosslinking agent)
The cohesive force and heat resistance can be improved by using an epoxy-based crosslinking agent in the pressure-sensitive adhesive composition of the present invention. Examples of the epoxy crosslinking agent include 1.3-bis (N, N-glycidylaminomethyl) cyclohexane (Tetrad C manufactured by Mitsubishi Gas Chemical Company), 1.3-bis (N, N-glycidylaminomethyl) benzene (Mitsubishi Gas). Known epoxy crosslinking agents such as Tetrad X) manufactured by Kagaku Co., Ltd. can be used.
架橋度合いの指標として、粘着剤層をトルエンに２４時間浸漬した後の不溶分を測定するゲル分率の値が用いられる。本発明の粘着剤組成物の架橋後のゲル分率は、２５％〜６０％が好ましい。またより好ましくは３０％〜５０％である。尚、ゲル分率の値は、無機フィラーの添加量を差し引いた樹脂の不溶分をさす。当該範囲とすることで、架橋後の粘着剤層に応力が加わった際にも、アクリル系共重合体と無機フィラーとの間の剥離が生じにくく、良好な粘着物性を得やすく、また、好適な初期接着性を得やすくなる。 As an index of the degree of cross-linking, the value of the gel fraction for measuring the insoluble content after the pressure-sensitive adhesive layer is immersed in toluene for 24 hours is used. The gel fraction after crosslinking of the pressure-sensitive adhesive composition of the present invention is preferably 25% to 60%. More preferably, it is 30% to 50%. In addition, the value of a gel fraction refers to the insoluble part of resin which deducted the addition amount of the inorganic filler. By adopting the range, even when stress is applied to the pressure-sensitive adhesive layer after crosslinking, peeling between the acrylic copolymer and the inorganic filler hardly occurs, and it is easy to obtain good pressure-sensitive adhesive properties. Easy initial adhesion.
（分散剤）
本発明の粘着剤組成物には、分散性を向上させるためアミン系の分散剤等を使用する。本発明においては、アミン系の分散剤を使用することで、エポキシ系架橋剤の架橋阻害を生じることなく好適な接着性を有する粘着剤層を形成できる。また、アクリル系の粘着剤組成物中に多量の無機フィラーを使用した場合にも、好適に無機フィラーを分散でき、かつ、保管時に無機フィラーが沈降した場合にも、凝集して再分散できないケーキング状態の発生を好適に防止できる。なかでも、アミン化が５以上のアミン系分散剤を好ましく使用でき、１０〜１５０がより好ましく、２０〜８０がさらに好ましい。アミン系の分散剤としては、例えば、ビックケミージャパン社製ＢＹＫ−１１２、ＢＹＫ−２００８等が挙げられる。
(Dispersant)
In the pressure-sensitive adhesive composition of the present invention, an amine-based dispersant or the like is used to improve dispersibility. In the present invention, by using an amine-based dispersant, a pressure-sensitive adhesive layer having suitable adhesiveness can be formed without causing cross-linking inhibition of the epoxy-based cross-linking agent. In addition, even when a large amount of inorganic filler is used in the acrylic pressure-sensitive adhesive composition, the inorganic filler can be suitably dispersed, and even when the inorganic filler settles during storage, caking that cannot be aggregated and redispersed. The occurrence of the state can be suitably prevented. Among these, an amine dispersant having an amination of 5 or more can be preferably used, more preferably 10 to 150, and still more preferably 20 to 80. Examples of amine-based dispersants include BYK-112 and BYK-2008 manufactured by BYK Japan.
粘着剤組成物への分散剤の添加量としては、エポキシ系架橋剤の架橋阻害が無く、良好なケーキング防止効果や接着性を実現するために、アクリル系共重合体１００質量部に対し固形分で３〜５質量部が好ましい。アミン系分散剤の添加量を当該範囲とすることで、得られる粘着剤層の凝集力を確保しやすく、また、無機フィラーの良好な分散性や耐ケーキング性を得やすいことから、特に好適な保持力や接着性を実現できる。 The amount of the dispersant added to the pressure-sensitive adhesive composition is such that there is no cross-linking inhibition of the epoxy-based cross-linking agent, and in order to realize a good anti-caking effect and adhesion, 3 to 5 parts by mass is preferable. By making the addition amount of the amine dispersant within this range, it is easy to ensure the cohesive strength of the resulting pressure-sensitive adhesive layer, and it is easy to obtain good dispersibility and caking resistance of the inorganic filler, which is particularly preferable. Holding power and adhesion can be realized.
また、本発明の粘着剤組成物は、熱伝導性、難燃性、粘着物性を大きく阻害しない範囲内で、老化防止剤、着色剤などの添加剤を適宜使用してもよい。 In addition, the pressure-sensitive adhesive composition of the present invention may appropriately use additives such as an anti-aging agent and a colorant as long as the thermal conductivity, flame retardancy, and pressure-sensitive adhesive properties are not significantly impaired.
本発明の粘着剤組成物からなる粘着剤層は損失正接のピークを示す温度が−４０℃以上、−１０℃以下であることが好ましい。当該範囲とすることで、無機フィラーを多く配合しても粘着剤の流動性と凝集性を両立しやすくなる。なお、損失正接のピーク温度は、５ｍｍ厚にまで重ね合わせた粘着剤層を試験片とし、レオメトリックス社製粘弾性試験機アレス２ｋＳＴＤに直径７．９ｍｍのパラレルプレートを装着し、試験片を挟み込み周波数１Ｈｚ、温度分散法で測定した値である。 The pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention preferably has a temperature at which the loss tangent peak is -40 ° C or higher and -10 ° C or lower. By setting it as the said range, even if it mix | blends many inorganic fillers, it will become easy to make the fluidity | liquidity and cohesion of an adhesive compatible. The peak temperature of loss tangent is 5 mm thick. The test piece is an adhesive layer, a rheometer viscoelasticity tester Ares 2kSTD is attached to a parallel plate with a diameter of 7.9 mm, and the test piece is sandwiched. This is a value measured by a frequency 1 Hz frequency dispersion method.
（粘着剤製造方法）
本発明の粘着剤組成物の製造方法として、前述の製造方法でアクリル系共重合体を製造した後に、必要に応じて粘着付与樹脂及び粘度調整用に酢酸エチル、ヘキサン、ＭＥＫなどの有機溶剤を添加し、粘着付与樹脂を溶解させながら混合し、得られた樹脂組成物を取り出す。次に得られた樹脂組成物と無機フィラー及びその他添加剤とを、プラネタリーミキサーなどの低速攪拌機を用い、樹脂組成物、無機フィラー及びその他添加剤が均一になるまで混合し、粘着剤組成物を得る。
(Adhesive manufacturing method)
As a manufacturing method of the pressure-sensitive adhesive composition of the present invention, after manufacturing an acrylic copolymer by the above-described manufacturing method, an organic solvent such as ethyl acetate, hexane, or MEK is used for adjusting the tackifier resin and viscosity as necessary. Add and mix while dissolving the tackifying resin and take out the resulting resin composition. Next, the obtained resin composition and the inorganic filler and other additives are mixed using a low-speed stirrer such as a planetary mixer until the resin composition, the inorganic filler and other additives are uniform, and an adhesive composition Get.
［粘着テープ］
本発明の粘着テープは、前述の粘着剤組成物からなる粘着剤層を有する粘着テープである。本発明の粘着テープは、基材を有する粘着テープであっても基材を有さない粘着剤層のみからなる粘着テープであってもよい。基材を有する粘着テープは、取り扱い性や加工性が良好であり、また基材を有さない粘着剤層のみからなる粘着テープは、熱伝導性や難燃性の効果を得やすいため、目的とする用途等に応じて適宜選択すればよい。
[Adhesive tape]
The pressure-sensitive adhesive tape of the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive composition. The pressure-sensitive adhesive tape of the present invention may be a pressure-sensitive adhesive tape having a base material or a pressure-sensitive adhesive tape comprising only a pressure-sensitive adhesive layer having no base material. The pressure-sensitive adhesive tape having a base material has good handleability and processability, and the pressure-sensitive adhesive tape consisting only of the pressure-sensitive adhesive layer having no base material is easy to obtain effects of thermal conductivity and flame retardancy. What is necessary is just to select suitably according to the use etc. to make.
基材を有する粘着テープとする場合には、基材として、フィルム、不織布、金属箔などを基材として使用できる。なかでもフィルム基材は取り扱い性等に優れるため好ましく使用でき、フィルム基材としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッソ樹脂フィルム、ナイロンフィルム、アクリル樹脂フィルム等の樹脂フィルム基材を挙げることができる。 When it is set as the adhesive tape which has a base material, a film, a nonwoven fabric, metal foil, etc. can be used as a base material as a base material. Among them, the film substrate is preferably used because it is excellent in handleability and the like. Examples of the film substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, and triacetyl cellulose. Film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film , Polyethersulfone film, polyetherimide film, polyimide film, Tsu Seo resin film, nylon film, mention may be made of resin film base material such as an acrylic resin film.
基材の片面に粘着剤組成物を貼合させた場合は片面粘着テープとして、基材の両側に粘着剤を貼合した場合は両面粘着テープとなる。基材は熱伝導性や難燃性を阻害させないことを考慮し、材質や厚さを選択する必要がある。特に両面粘着テープの基材として、ＰＥＴフィルムは強度、絶縁性、難燃性、平滑性、均一な厚さなどの性能面に加え、生産性、入手性の面から好ましい。ＰＥＴフィルム表面には粘着剤の投錨性を向上させるためにコロナ処理または易接着処理していることが好ましい。 When the adhesive composition is bonded to one side of the substrate, it becomes a single-sided adhesive tape, and when the adhesive is bonded to both sides of the substrate, it becomes a double-sided adhesive tape. It is necessary to select the material and thickness of the base material in consideration of not inhibiting thermal conductivity and flame retardancy. In particular, as a base material for a double-sided pressure-sensitive adhesive tape, a PET film is preferable from the viewpoints of productivity and availability in addition to performance aspects such as strength, insulation, flame retardancy, smoothness and uniform thickness. The PET film surface is preferably subjected to corona treatment or easy adhesion treatment in order to improve the anchoring property of the pressure-sensitive adhesive.
基材の厚さは、樹脂フィルムの場合、３μｍ〜５０μｍであることが好ましく、さらに好ましくは６〜２５μｍが好ましい。当該範囲とすることで、熱伝導性、難燃性を阻害することなく、且つ良好な取り扱い性や加工性を得ることができる。 In the case of a resin film, the thickness of the substrate is preferably 3 μm to 50 μm, more preferably 6 to 25 μm. By setting it as the said range, favorable handleability and workability can be obtained, without inhibiting heat conductivity and a flame retardance.
粘着剤層の厚さは、１回の乾燥後塗工厚さで１０μｍ〜１５０μｍであることが好ましい。当該範囲とすることで、粘着物性を好適に確保しやすく、また、製造時の粘着剤中の希釈溶剤の乾燥が容易となり生産性を向上させやすくなる。 The thickness of the pressure-sensitive adhesive layer is preferably 10 μm to 150 μm as a coating thickness after drying once. By setting it as the said range, it is easy to ensure adhesive physical property suitably, and it becomes easy to dry the dilution solvent in the adhesive at the time of manufacture, and it becomes easy to improve productivity.
粘着テープの厚さは、特に両面粘着テープの場合、２０μｍ〜３００μｍであることが好ましい。より好ましくは５０μｍ〜２５０μｍである。粘着テープが１５０μｍを超える場合は、２回の塗工工程を経て粘着剤層を積層する等の方法により厚膜形成が可能である。積層時に各粘着剤層の間に基材を貼合すれば基材を有する両面粘着テープとなる。なお、片面テープの場合、粘着剤層の厚さと基材の厚さを足したものが粘着テープ厚さとなる。 The thickness of the adhesive tape is preferably 20 μm to 300 μm, particularly in the case of a double-sided adhesive tape. More preferably, it is 50 micrometers-250 micrometers. When the pressure-sensitive adhesive tape exceeds 150 μm, a thick film can be formed by a method such as laminating a pressure-sensitive adhesive layer through two coating steps. If a base material is bonded between each adhesive layer at the time of lamination | stacking, it will become a double-sided adhesive tape which has a base material. In the case of a single-sided tape, the thickness of the pressure-sensitive adhesive layer plus the thickness of the base material is the pressure-sensitive adhesive tape thickness.
粘着テープの製造方法は、基材を使用しない場合は剥離ライナーなどの支持体に粘着剤組成物をロールコーターやダイコーターなどで一定の厚さで塗布し、ドライヤーで希釈溶剤を乾燥させ、他の剥離ライナーを貼合させる方法により製造できる。両面に剥離処理を施した剥離ライナーを使用した場合は、前述と同様に粘着剤組成物を剥離ライナーに塗布、乾燥した後にそのままロール状に巻き取り製造することができる。
基材を使用する際は前述と同様に粘着剤組成物を剥離ライナーに塗布、乾燥した後に基材の片側に貼合することで片面粘着テープが製造できる。更に剥離ライナーに熱伝導性粘着剤を塗布、乾燥したものを基材のもう一方の側に貼合することで両面粘着テープが製造できる。
When the base material is not used, the pressure-sensitive adhesive tape is manufactured by applying the pressure-sensitive adhesive composition to a support such as a release liner with a constant thickness using a roll coater or die coater, drying the diluted solvent with a dryer, etc. It can manufacture by the method of bonding the release liner of. When a release liner that has been subjected to a release treatment on both sides is used, the pressure-sensitive adhesive composition can be applied to the release liner and dried in the same manner as described above, and then wound into a roll.
When using a base material, a single-sided adhesive tape can be manufactured by apply | coating an adhesive composition to a release liner like the above, and drying and then bonding to the one side of a base material. Furthermore, a double-sided pressure-sensitive adhesive tape can be produced by applying a thermally conductive pressure-sensitive adhesive to a release liner and bonding the dried liner to the other side of the substrate.
粘着剤組成物中の無機フィラーとして、熱伝導難燃性フィラーを使用した熱伝導難燃性粘着剤組成物を使用した本発明の粘着テープ及び両面粘着テープは、特に液晶画像表示のバックライト等に使用されるＬＥＤ光源の固定に特に好適に使用できる。ＬＥＤ光源の固定は熱伝導性材料、例えば、アルミニウム等の金属材料へ固定することで、より好適な放熱性を実現できる。 As the inorganic filler in the pressure-sensitive adhesive composition, the pressure-sensitive adhesive tape and double-sided pressure-sensitive adhesive tape of the present invention using the heat-conductive flame-retardant pressure-sensitive adhesive composition using a heat-conductive flame-retardant filler are particularly used for backlights for liquid crystal image display, etc. It can be particularly suitably used for fixing the LED light source used in the above. The LED light source can be fixed to a heat conductive material, for example, a metal material such as aluminum, thereby realizing more suitable heat dissipation.
熱伝導難燃性フィラーを使用した粘着テープをＬＥＤ光源の固定に使用する場合には、粘着テープの熱伝導率は０．６Ｗ／ｍ・ｋ以上であることが好ましい。また、難燃性はＵｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．社の規格において、ＵＬ９４Ｖ−２またはＶＴＭ−２以上の性能であることが好ましく、ＵＬ９４Ｖ−０またはＶＴＭ−０以上であることが特に好ましい。更に粘着物性として、接着力は５Ｎ／２０ｍｍ幅以上、保持力は、５ｍｍ幅×３０ｍｍ長の面積で１００ｇの荷重をせん断方向にかけた際に２４時間保持する性能であることが好ましい。 When the adhesive tape using the heat conductive flame retardant filler is used for fixing the LED light source, the thermal conductivity of the adhesive tape is preferably 0.6 W / m · k or more. In addition, flame retardancy is reported by Underwriters Laboratories Inc. According to the company standard, the performance is preferably UL94V-2 or VTM-2 or higher, particularly preferably UL94V-0 or VTM-0 or higher. Furthermore, as adhesive properties, it is preferable that the adhesive strength is 5 N / 20 mm width or more, and the holding power is a performance of holding for 24 hours when a load of 100 g is applied in the shear direction in an area of 5 mm width × 30 mm length.
［実施例１］
（１−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、２−エチルヘキシルアクリレート９６．４質量部、β−カルボキシエチルアクリレート２．４質量部、アクリル酸１．２質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓ、重量平均分子量５０万であるアクリル重合体溶液を得た。
[Example 1]
(1-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 96.4 parts by mass of 2-ethylhexyl acrylate, 2.4 parts by mass of β-carboxyethyl acrylate Part, 1.2 parts by mass of acrylic acid and 98 parts by mass of ethyl acetate were added, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. An acrylic polymer solution having a nonvolatile content of 50% by mass, a viscosity of 8000 mPa · s, and a weight average molecular weight of 500,000 was obtained.
（１−２）粘着剤組成物の調整
プラネタリーミキサーの容器に無機フィラーとして熱伝導難燃性の水酸化アルミニウム（昭和電工社製ハイジライトＨ３２、平均粒径８μｍ）を粘着剤組成物固形分１００質量部に対し２５０質量部およびアミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−１１２を粘着剤組成物固形分１００に対して固形分で４質量部加えた後、得られた粘着剤組成物を加える。３０分攪拌させ水酸化アルミニウムと分散剤、粘着剤組成物を均一に混合させた。酢酸エチルを加え固形分７０％になるよう調整し、粘度１２０００ｍＰａ・ｓの熱伝導難燃性粘着剤組成物を得た。
(1-2) Adjustment of pressure-sensitive adhesive composition Heat conductive flame retardant aluminum hydroxide (Hijilite H32, Showa Denko Co., Ltd., average particle size: 8 μm) as an inorganic filler in a container of a planetary mixer After adding 4 parts by mass of 100 parts by mass of DISPERBYK-112 manufactured by Big Chemie Japan Co., Ltd. and 100 parts by mass of the solid content to the adhesive composition solids 100, the resulting adhesive composition was obtained. Add. The mixture was stirred for 30 minutes to uniformly mix aluminum hydroxide, a dispersant, and a pressure-sensitive adhesive composition. Ethyl acetate was added to adjust the solid content to 70% to obtain a heat conductive flame retardant pressure-sensitive adhesive composition having a viscosity of 12000 mPa · s.
（１−３）粘着テープの調整
（１−２）で得られた熱伝導難燃性粘着剤組成物にエポキシ系架橋剤（三菱ガス化学社製テトラッドＣ）２％酢酸エチル溶液を熱伝導難燃性粘着剤組成物中のアクリル共重合体固形分１００部に対して、２．１部配合し、ディゾルバー攪拌機で３０分間攪拌した。得られた粘着剤組成物を剥離ライナーに乾燥後厚さが１１０μｍになるようにロールコーターで塗布し、８０℃ドライヤー中で３分間乾燥させた。得られた粘着シートを表面にコロナ処理を施した厚さ３０μｍのポリイミドコートＰＥＴフィルム（東レ社製ルミラーＺＶ７０）の両側にラミネートし、厚さ２５０μｍの両面粘着テープを作成した。架橋剤の架橋反応のため４０℃乾燥機に４８時間養生させ両面粘着テープを得た。
(1-3) Adjustment of pressure-sensitive adhesive tape An epoxy-based crosslinking agent (Tetrad C, manufactured by Mitsubishi Gas Chemical Company) 2% ethyl acetate solution is difficult to heat-conductive to the heat-conductive flame-retardant pressure-sensitive adhesive composition obtained in (1-2). 2.1 parts of 100 parts of the acrylic copolymer solid content in the flammable pressure-sensitive adhesive composition were blended and stirred with a dissolver stirrer for 30 minutes. The obtained pressure-sensitive adhesive composition was applied to a release liner with a roll coater so as to have a thickness of 110 μm after drying, and dried in an 80 ° C. dryer for 3 minutes. The obtained pressure-sensitive adhesive sheet was laminated on both sides of a 30 μm-thick polyimide-coated PET film (Lumirror ZV70 manufactured by Toray Industries, Inc.) whose surface was subjected to corona treatment, to prepare a double-sided pressure-sensitive adhesive tape having a thickness of 250 μm. A double-sided pressure-sensitive adhesive tape was obtained by curing in a 40 ° C. dryer for 48 hours for the crosslinking reaction of the crosslinking agent.
［実施例２］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−２００８を使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Example 2]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the dispersant, DISPERBYK-2008 manufactured by Big Chemie Japan, was used as the dispersant.
［実施例３］
（３−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、２−エチルヘキシルアクリレート３０．０質量部、ブチルアクリレート６３．４質量部、アクリル酸３．０質量部、酢酸ビニル３．５質量部、β―ヒドロキシエチルアクリレート０．１質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓ、重量平均分子量５０万であるアクリル重合体溶液を得た。
得られたアクリル共重合体溶液を用いて（１−２）粘着剤組成物の調整に記載の方法にて調整を行った。得られた熱伝導難燃性粘着剤組成物を用いて（１−３）粘着テープの調整に記載の方法にて調整を行った。
[Example 3]
(3-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 30.0 parts by mass of 2-ethylhexyl acrylate, 63.4 parts by mass of butyl acrylate, acrylic 3.0 parts by weight of acid, 3.5 parts by weight of vinyl acetate, 0.1 part by weight of β-hydroxyethyl acrylate and 98 parts by weight of ethyl acetate were charged, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. An acrylic polymer solution having a nonvolatile content of 50% by mass, a viscosity of 8000 mPa · s, and a weight average molecular weight of 500,000 was obtained.
It adjusted by the method as described in (1-2) adjustment of an adhesive composition using the obtained acrylic copolymer solution. It adjusted by the method as described in (1-3) adjustment of an adhesive tape using the obtained heat conductive flame-retardant adhesive composition.
［実施例４］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−２００８を使用したこと以外は、実施例３と同様に両面粘着テープを得た。
[Example 4]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as Example 3, except that DISPERBYK-2008 manufactured by Big Chemie Japan Co., Ltd. was used as the dispersant.
［実施例５］
（５−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ブチルアクリレート９３．４質量部、アクリル酸３．５質量部、酢酸ビニル３．０質量部、β―ヒドロキシエチルアクリレート０．１質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓ、重量平均分子量５０万であるアクリル重合体溶液を得た。
得られたアクリル共重合体溶液を用いて（１−２）粘着剤組成物の調整に記載の方法にて調整を行った。得られた熱伝導難燃性粘着剤組成物を用いて（１−３）粘着テープの調整に記載の方法にて調整を行った。
[Example 5]
(5-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 93.4 parts by mass of butyl acrylate, 3.5 parts by mass of acrylic acid, vinyl acetate 3 0.0 parts by mass, 0.1 parts by mass of β-hydroxyethyl acrylate, and 98 parts by mass of ethyl acetate were charged, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. An acrylic polymer solution having a nonvolatile content of 50% by mass, a viscosity of 8000 mPa · s, and a weight average molecular weight of 500,000 was obtained.
It adjusted by the method as described in (1-2) adjustment of an adhesive composition using the obtained acrylic copolymer solution. It adjusted by the method as described in (1-3) adjustment of an adhesive tape using the obtained heat conductive flame-retardant adhesive composition.
［実施例６］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−２００８を使用したこと以外は、実施例３と同様に両面粘着テープを得た。
[Example 6]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as Example 3, except that DISPERBYK-2008 manufactured by Big Chemie Japan Co., Ltd. was used as the dispersant.
［実施例７］
水酸化アルミニウムの含有量を粘着剤組成物固形分１００質量部に対し２７０質量部とした以外は実施例１と同様にして両面粘着テープを得た。
[Example 7]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the content of aluminum hydroxide was 270 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.
［実施例８］
水酸化アルミニウムの含有量を粘着剤組成物固形分１００質量部に対し２２０質量部とした以外は実施例１と同様にして両面粘着テープを得た。
[Example 8]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the content of aluminum hydroxide was 220 parts by weight with respect to 100 parts by weight of the solid content of the pressure-sensitive adhesive composition.
［実施例９］
水酸化アルミニウムの含有量を粘着剤組成物固形分１００質量部に対し２００質量部とした以外は実施例１と同様にして両面粘着テープを得た。
[Example 9]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the content of aluminum hydroxide was 200 parts by weight with respect to 100 parts by weight of the solid content of the pressure-sensitive adhesive composition.
［実施例１０］
水酸化アルミニウムの含有量を粘着剤組成物固形分１００質量部に対し２４０質量部とした以外は実施例１と同様にして、熱伝導難燃性粘着剤組成物を得た。得られた熱伝導難燃性粘着剤組成物にエポキシ系架橋剤（三菱ガス化学社製テトラッドＣ）２％酢酸エチル溶液を熱伝導難燃性粘着剤組成物中のアクリル共重合体固形分１００部に対して、２．１部配合し、ディゾルバー攪拌機で３０分間攪拌した。得られた粘着剤組成物を剥離ライナーに乾燥後厚さが６０μｍになるようにロールコーターで塗布し、８０℃ドライヤー中で３分間乾燥させた。得られた粘着シートを表面にコロナ処理を施した厚さ６μｍのＰＥＴフィルムの両側にラミネートし、厚さ１２５μｍの両面粘着テープを作成した。架橋剤の架橋反応のため４０℃乾燥機に４８時間養生させ両面粘着テープを得た。
[Example 10]
A thermally conductive flame-retardant pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the content of aluminum hydroxide was 240 parts by weight with respect to 100 parts by weight of the solid content of the pressure-sensitive adhesive composition. An epoxy-based crosslinking agent (Tetrad C manufactured by Mitsubishi Gas Chemical Company) 2% ethyl acetate solution was added to the obtained heat conductive flame retardant pressure-sensitive adhesive composition, and the acrylic copolymer solid content in the heat conductive flame retardant pressure-sensitive adhesive composition was 100. 2.1 parts with respect to parts, and stirred for 30 minutes with a dissolver stirrer. The obtained pressure-sensitive adhesive composition was applied to a release liner with a roll coater so that the thickness after drying was 60 μm, and dried in an 80 ° C. dryer for 3 minutes. The obtained pressure-sensitive adhesive sheet was laminated on both sides of a 6 μm-thick PET film having a corona treatment on the surface to prepare a double-sided pressure-sensitive adhesive tape having a thickness of 125 μm. A double-sided pressure-sensitive adhesive tape was obtained by curing in a 40 ° C. dryer for 48 hours for the crosslinking reaction of the crosslinking agent.
［実施例１１］
水酸化アルミニウムの含有量を粘着剤組成物固形分１００質量部に対し２６０質量部とした以外は実施例１０と同様にして両面粘着テープを得た。
[Example 11]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 10 except that the content of aluminum hydroxide was 260 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.
［実施例１２］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−１０８を使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Example 12]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the dispersant, DISPERBYK-108 manufactured by Big Chemie Japan, was used as the dispersant.
［実施例１３］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−１６４を使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Example 13]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that DISPERBYK-164 manufactured by Big Chemie Japan Co., Ltd. was used as the dispersant.
［実施例１４］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−２１６４を使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Example 14]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as Example 1, except that DISPERBYK-2164 manufactured by Big Chemie Japan Co., Ltd. was used as the dispersant.
［実施例１５］
分散剤として、アミン系分散剤ビックケミージャパン社製ＤＩＳＰＥＲＢＹＫ−１６７を使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Example 15]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that DISPERBYK-167 manufactured by Big Chemie Japan Co., Ltd. was used as the dispersant.
［実施例１６］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例１と同様にして両面粘着テープを得た。
[Example 16]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that heat-conducting flame-retardant low soda type aluminum hydroxide (Hijilite H32I manufactured by Showa Denko KK, average particle size: 8 μm) was used as the inorganic filler.
［実施例１７］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例２と同様にして両面粘着テープを得た。
[Example 17]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 2 except that heat-conducting flame retardant low soda type aluminum hydroxide (Hijilite H32I manufactured by Showa Denko KK, average particle size 8 μm) was used as the inorganic filler.
［実施例１８］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例１２と同様にして両面粘着テープを得た。
[Example 18]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 12 except that heat-conducting flame retardant low soda type aluminum hydroxide (Hijilite H32I manufactured by Showa Denko KK, average particle size: 8 μm) was used as the inorganic filler.
［実施例１９］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例１３と同様にして両面粘着テープを得た。
[Example 19]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 13 except that heat-conducting flame-retardant low soda type aluminum hydroxide (Showa Denko Hijilite H32I, average particle size 8 μm) was used as the inorganic filler.
［実施例２０］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例１４と同様にして両面粘着テープを得た。
[Example 20]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 14 except that heat-conducting flame-retardant low soda type aluminum hydroxide (Hijilite H32I manufactured by Showa Denko KK, average particle size: 8 μm) was used as the inorganic filler.
［実施例２１］
無機フィラーとして熱伝導難燃性の低ソーダタイプ水酸化アルミニウム（昭和電工社製ハイジライトＨ３２Ｉ、平均粒径８μｍ）を使用したこと以外は実施例１５と同様にして両面粘着テープを得た。
[Example 21]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 15 except that heat-conducting flame-retardant low soda type aluminum hydroxide (Hijilite H32I manufactured by Showa Denko KK, average particle size: 8 μm) was used as the inorganic filler.
［比較例１］
分散剤として、リン酸系分散剤ビックケミージャパン社製ＢＹＫ−１１１を粘着剤組成物固形分１００に対して固形分で６質量部使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Comparative Example 1]
As a dispersant, a double-sided pressure-sensitive adhesive tape was used in the same manner as in Example 1 except that 6 parts by mass of the phosphoric acid dispersant BYK-111 manufactured by Big Chemy Japan Co., Ltd. was used in solid content with respect to the solid content 100 of the adhesive composition. Obtained.
［比較例２］
分散剤として、リン酸塩系分散剤ビックケミージャパン社製ＢＹＫ−１８０を粘着剤組成物固形分１００に対して固形分で２質量部使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Comparative Example 2]
Double-sided pressure-sensitive adhesive tape as in Example 1 except that BYK-180, a phosphate-based dispersant, Big Chemie Japan Co., as a dispersant, was used in an amount of 2 parts by mass with respect to the solid content 100 of the adhesive composition. Got.
［比較例３］
分散剤として、リン酸塩系分散剤ビックケミージャパン社製ＢＹＫ−１８０を粘着剤組成物固形分１００に対して固形分で３質量部使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Comparative Example 3]
Double-sided pressure-sensitive adhesive tape as in Example 1 except that BYK-180, a phosphate-based dispersant, Big Chemie Japan Co., as a dispersant, was used in an amount of 3 parts by mass with respect to the solid content 100 of the adhesive composition. Got.
［比較例４］
分散剤として、リン酸１／２中和塩系分散剤ビックケミージャパン社製ＢＹＫ−１０６を粘着剤組成物固形分１００に対して固形分で４質量部使用したこと以外は、実施例１と同様に両面粘着テープを得た。
[Comparative Example 4]
As a dispersant, Example 1 except that 4 parts by mass of the phosphoric acid 1/2 neutralized salt-based dispersant BYK-106 manufactured by Big Chemie Japan Co., Ltd. was used in a solid content of 100 parts by mass relative to the solid content 100 of the pressure-sensitive adhesive composition. Similarly, a double-sided adhesive tape was obtained.
上記実施例及び比較例にて得られた粘着剤組成物及び両面粘着テープにつき、下記評価を行った。得られた結果を下表に示した。 The following evaluation was performed about the adhesive composition and double-sided adhesive tape obtained by the said Example and comparative example. The results obtained are shown in the table below.
［ゲル分率］
上記実施例及び比較例にて得られた粘着テープを４０ｍｍ×５０ｍｍに切断した試料を天秤で重量を測定し、トルエンに浸漬し常温下で２４時間静置した。浸漬後に試料をとりだし、乾燥機で１０５℃で１時間乾燥させ、室温で冷却した後に試料の重量を測定した。トルエン浸漬後の試料重量をトルエン浸漬前の試料重量で除して不溶分の割合を百分立で求めた。
[Gel fraction]
Samples obtained by cutting the adhesive tapes obtained in the above Examples and Comparative Examples into 40 mm × 50 mm were weighed with a balance, immersed in toluene, and allowed to stand at room temperature for 24 hours. After immersion, the sample was taken out, dried at 105 ° C. for 1 hour with a drier, cooled at room temperature, and the weight of the sample was measured. The weight of the sample after immersion in toluene was divided by the weight of the sample before immersion in toluene, and the proportion of insoluble matter was determined as a percentage.
［熱伝導率］
上記実施例及び比較例にて得られた粘着テープを空気を巻き込まないように５００μｍになるまで貼り重ねせた。最外面は厚さ６μｍのＰＥＴフィルムを貼合した。得られた試料を５ｃｍ×１５ｃｍに切断して測定用試料を作製した。得られた測定用試料を京都電子工業性熱伝導率測定機ＱＴＭ−５００と、薄膜法測定用ソフトＱＴＭ−５Ｗを使用し測定を行った。
[Thermal conductivity]
The pressure-sensitive adhesive tapes obtained in the above examples and comparative examples were laminated to 500 μm so as not to entrain air. The outermost surface was bonded with a PET film having a thickness of 6 μm. The obtained sample was cut into 5 cm × 15 cm to prepare a measurement sample. The obtained measurement sample was measured using a Kyoto Electronics Industrial thermal conductivity measuring device QTM-500 and a thin film method measurement software QTM-5W.
［難燃性］
上記実施例及び比較例にて得られた粘着テープをＵｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．社ＵＬ９４ＶＴＭの規格に準じて試験を行った。なお、基材を有さない粘着テープは、筒状の形成が困難なため同社ＵＬ９４Ｖの規格に準じて試験を行った。
難燃性のクラスは下表により判定した。
The adhesive tapes obtained in the above examples and comparative examples were obtained from Underwriters Laboratories Inc. The test was conducted according to the standard of UL94VTM. In addition, since the adhesive tape which does not have a base material cannot form a cylinder shape, it tested according to the specification of the company UL94V.
The flame retardancy class was determined according to the following table.
［９０°ピール接着力］
上記実施例及び比較例にて得られた粘着テープの片面に厚さ５０μｍのアルミ箔を貼合し２０ｍｍ幅に切断した。２３℃５０％ＲＨ雰囲気下でもう一方の粘着面をアルミ板に２ｋｇローラー１往復の加圧条件で貼付し、１時間静置後に９０°方向へ３００ｍｍ／分の速度で引き剥がした際の接着力を測定した。
[90 ° peel adhesion]
An aluminum foil having a thickness of 50 μm was bonded to one side of the pressure-sensitive adhesive tape obtained in the above examples and comparative examples, and cut into a width of 20 mm. Adhesion when the other adhesive surface is affixed to an aluminum plate under a reciprocating pressure of 2 kg roller in a reciprocating atmosphere at 23 ° C and 50% RH, and left for 1 hour and then peeled off at a rate of 300 mm / min in the 90 ° direction. The force was measured.
［保持力］
上記実施例及び比較例にて得られた粘着テープを５ｍｍ幅×３０ｍｍ長さとした試料を、厚さ５００μｍのアルミ板の片端に貼付した。２３℃５０％ＲＨ雰囲気下でもう一方の粘着面をアルミ板に貼付し、５ｋｇローラー１往復１往復の加圧条件で貼付し、１時間静置した。静置後に８５℃雰囲気下でせん断方向に１００ｇの荷重をかけ、試料が剥がれ落下するまでの時間を測定した。２４時間後に試料の落下が無かった場合は試験を終了し２４時間以上（＞２４）と記載した。
[Retention force]
The sample which made the adhesive tape obtained in the said Example and comparative example 5 mm width x 30 mm length was affixed on the one end of the 500-micrometer-thick aluminum plate. The other adhesive surface was affixed to an aluminum plate in an atmosphere of 23 ° C. and 50% RH, affixed under a pressure condition of one reciprocation and one reciprocation of a 5 kg roller, and allowed to stand for 1 hour. After standing, a load of 100 g was applied in the shear direction in an atmosphere at 85 ° C., and the time until the sample peeled off and dropped was measured. When the sample did not fall after 24 hours, the test was terminated and it was described as 24 hours or longer (> 24).
［ケーキング］
上記実施例及び比較例にて得られた熱伝導難燃性粘着剤組成物を２２５ＣＣのガラス瓶に密閉状態で１週間静置した。静置後にガラス瓶の底に沈降している無機フィラーの凝集状態をスパチュラにて確認した。ケーキングがある状態とは、スパチュラによる再分散が困難または再分散不可の状態のことである。
[Caking]
The heat conductive flame-retardant pressure-sensitive adhesive composition obtained in the above Examples and Comparative Examples was allowed to stand in a sealed state in a glass bottle of 225CC for 1 week. The aggregation state of the inorganic filler settled on the bottom of the glass bottle after standing was confirmed with a spatula. The state where there is caking is a state where redispersion with a spatula is difficult or impossible.
［架橋阻害］
上記実施例（１−１）にて得られたアクリル系共重合体に各分散剤をアクリル共重合体固形分１００部に対して、４質量部、エポキシ系架橋剤（三菱ガス化学社製テトラッドＣ）２％酢酸エチル溶液をアクリル共重合体固形分１００部に対して、２．１部配合し、ディゾルバー攪拌機で３０分間攪拌する。得られた粘着剤組成物を剥離ライナーに乾燥後厚さが１１０μｍになるようにロールコーターで塗布し、８０℃ドライヤー中で３分間乾燥させる。得られた粘着シートを表面にコロナ処理を施した厚さ２５μｍのＰＥＴフィルムの両側にラミネートし、厚さ２４５μｍの両面粘着テープを作成した。架橋剤の架橋反応のため４０℃乾燥機に４８時間養生させ両面粘着テープを得た。得られた両面粘着テープを用いて、ゲル分率を測定した。分散剤を添加していない両面粘着テープのゲル分率よりも１０％以上低下したものを架橋阻害有りとした。
[Inhibition of cross-linking]
In the acrylic copolymer obtained in the above Example (1-1), 4 parts by mass of each dispersing agent with respect to 100 parts of the acrylic copolymer solid content, an epoxy crosslinking agent (Tetrad manufactured by Mitsubishi Gas Chemical Co., Ltd.) C) 2.1 parts of a 2% ethyl acetate solution is blended with 100 parts of the acrylic copolymer solid content, and stirred with a dissolver stirrer for 30 minutes. The obtained pressure-sensitive adhesive composition is applied to a release liner with a roll coater so as to have a thickness of 110 μm after drying, and dried in an 80 ° C. dryer for 3 minutes. The obtained pressure-sensitive adhesive sheet was laminated on both sides of a 25 μm-thick PET film having a corona treatment on the surface to prepare a double-sided pressure-sensitive adhesive tape having a thickness of 245 μm. A double-sided pressure-sensitive adhesive tape was obtained by curing in a 40 ° C. dryer for 48 hours for the crosslinking reaction of the crosslinking agent. The gel fraction was measured using the obtained double-sided pressure-sensitive adhesive tape. Those having a gel fraction of 10% or more lower than the gel fraction of the double-sided pressure-sensitive adhesive tape to which no dispersant was added were regarded as having crosslinking inhibition.
上記表から明らかなように、実施例１〜２１の本願発明の粘着剤組成物は、多量の無機フィラーを添加した場合にも優れた接着性を実現でき、良好な難燃性や熱伝導性と、好適な接着性、熱伝導難燃性粘着剤組成物の保存安定性とを両立できるものであった。一方、比較例１の粘着剤組成物は、保持力に乏しく、良好な接着性能を実現できなかった。また、比較例２〜４の粘着剤組成物は、ケーキングが生じ、スパチュラによる再分散ができず粘着テープを形成できなかった。 As is clear from the above table, the pressure-sensitive adhesive compositions of the invention of Examples 1 to 21 can realize excellent adhesiveness even when a large amount of inorganic filler is added, and have good flame retardancy and thermal conductivity. And the storage stability of the preferred adhesiveness and heat conductive flame retardant pressure-sensitive adhesive composition. On the other hand, the pressure-sensitive adhesive composition of Comparative Example 1 was poor in holding power and could not realize good adhesive performance. Moreover, the pressure-sensitive adhesive compositions of Comparative Examples 2 to 4 caused caking and could not be redispersed with a spatula and could not form a pressure-sensitive adhesive tape.
Claims (7)
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| JP6404590B2 (en) * | 2014-04-18 | 2018-10-10 | 日東電工株式会社 | Double-sided adhesive sheet for portable electronic devices |
| JP2017043670A (en) * | 2015-08-25 | 2017-03-02 | 三菱マテリアル株式会社 | Vanadium dioxide fluid dispersion and vanadium dioxide paint |
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| JPH11269438A (en) * | 1998-03-25 | 1999-10-05 | Dainippon Ink & Chem Inc | Heat-conductive flame-retardant pressure-sensitive adhesive and pressure-sensitive adhesive tape |
| WO2000036039A2 (en) * | 1998-12-15 | 2000-06-22 | Avery Dennison Corporation | Pressure-sensitive adhesive compositions and pressure-sensitive adhesive label constructions exhibiting low adhesive residue in printers |
| JP4913932B2 (en) * | 1999-02-10 | 2012-04-11 | Ｄｉｃ株式会社 | Flame retardant pressure sensitive adhesive and flame retardant pressure sensitive adhesive tape |
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| JP5651344B2 (en) * | 2010-02-04 | 2015-01-14 | 日東電工株式会社 | Thermally conductive double-sided adhesive sheet |
| JP5454300B2 (en) * | 2010-03-30 | 2014-03-26 | 日立化成株式会社 | HEAT CONDUCTIVE SHEET, ITS MANUFACTURING METHOD, AND HEAT DISCHARGE DEVICE USING SAME |
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