JP2019182892A - Adhesive composition and connection structure - Google Patents
Adhesive composition and connection structure Download PDFInfo
- Publication number
- JP2019182892A JP2019182892A JP2018070659A JP2018070659A JP2019182892A JP 2019182892 A JP2019182892 A JP 2019182892A JP 2018070659 A JP2018070659 A JP 2018070659A JP 2018070659 A JP2018070659 A JP 2018070659A JP 2019182892 A JP2019182892 A JP 2019182892A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- compound
- electronic component
- acrylate
- film
- 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.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 135
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 134
- 239000000203 mixture Substances 0.000 title claims abstract description 107
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 31
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 18
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- -1 acrylate compound Chemical class 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 20
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 53
- 239000010408 film Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 16
- 239000012790 adhesive layer Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007373 indentation Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000021588 free fatty acids Nutrition 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
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([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
- 239000011133 lead Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000638 stimulation Effects 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
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- C09J7/35—Heat-activated
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
- H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
Abstract
Description
本発明は、接着剤組成物及び接続構造体に関する。 The present invention relates to an adhesive composition and a connection structure.
近年、電子部品と、配線基板との接着には、一般的に、エポキシ系化合物による重合反応を利用した接着剤、又はアクリレート系化合物による重合反応を利用した接着剤のいずれかが使用されることが一般的である。例えば、下記の特許文献１には、エポキシ系化合物を主体とするフィルム状の電子部品用接着剤が開示されている。 In recent years, either an adhesive using a polymerization reaction by an epoxy compound or an adhesive using a polymerization reaction by an acrylate compound is generally used for bonding an electronic component and a wiring board. Is common. For example, Patent Document 1 below discloses a film-like adhesive for electronic parts mainly composed of an epoxy compound.
一方、アクリレート系化合物は、エポキシ系化合物と比較して、低温でも高い反応性を示す。そのため、アクリレート系化合物を含有する接着剤は、例えば、熱を掛けたくない電子部品を接着する場合等に用いられ得る。 On the other hand, an acrylate compound exhibits higher reactivity even at a low temperature than an epoxy compound. Therefore, an adhesive containing an acrylate compound can be used, for example, when bonding an electronic component that does not want to be heated.
しかし、アクリレート系化合物を含有する接着剤は、エポキシ系化合物と比較して、湿熱環境下における信頼性試験で劣化が進行しやすかった。そのため、アクリレート系化合物を含有する接着剤において、接着信頼性をより高めることが求められていた。 However, the adhesive containing an acrylate compound was more likely to deteriorate in a reliability test in a humid heat environment than an epoxy compound. Therefore, it has been required to further improve the adhesion reliability in the adhesive containing the acrylate compound.
そこで、本発明は、上記問題に鑑みてなされたものであり、本発明の目的とするところは、より高い接着信頼性を有する、新規かつ改良された接着剤組成物及び接続構造体を提供することにある。 Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a new and improved adhesive composition and connection structure having higher adhesion reliability. There is.
上記課題を解決するために、本発明のある観点によれば、膜形成樹脂と、アクリレート系化合物と、重合開始剤と、カルボジイミド系化合物と、を含有し、前記膜形成樹脂又は前記アクリレート系化合物の少なくとも１つ以上は、カルボキシ基を有する化合物であり、前記カルボジイミド系化合物の含有量は、前記カルボキシ基を有する化合物の総質量に対して、０．１質量％以上１５０質量％以下である、接着剤組成物が提供される。 In order to solve the above-described problems, according to one aspect of the present invention, a film-forming resin, an acrylate-based compound, a polymerization initiator, and a carbodiimide-based compound are contained, and the film-forming resin or the acrylate-based compound is included. Is a compound having a carboxy group, and the content of the carbodiimide compound is 0.1% by mass or more and 150% by mass or less based on the total mass of the compound having a carboxy group. An adhesive composition is provided.
前記カルボジイミド系化合物の含有量は、前記カルボキシ基を有する化合物の総質量に対して、３０質量％以下であってもよい。 The content of the carbodiimide compound may be 30% by mass or less based on the total mass of the compound having a carboxy group.
前記カルボジイミド系化合物の含有量は、前記カルボキシ基を有する化合物の総質量に対して、５質量％以上であってもよい。 The content of the carbodiimide compound may be 5% by mass or more based on the total mass of the compound having a carboxy group.
前記膜形成樹脂は、ポリウレタン樹脂であってもよい。 The film forming resin may be a polyurethane resin.
前記膜形成樹脂の酸価は、１ＫＯＨｍｇ／ｇ以上であってもよい。 The acid value of the film-forming resin may be 1 KOHmg / g or more.
前記アクリレート系化合物は、（メタ）アクリレート樹脂であってもよい。 The acrylate compound may be a (meth) acrylate resin.
前記重合開始剤は、ラジカル系重合開始剤であってもよい。 The polymerization initiator may be a radical polymerization initiator.
前記接着剤組成物は、フィルム状に設けられてもよい。 The adhesive composition may be provided in a film shape.
前記接着剤組成物は、導電粒子をさらに含んでもよい。 The adhesive composition may further include conductive particles.
また、上記課題を解決するために、本発明の別の観点によれば、上記の接着剤組成物と、前記接着剤組成物を介して接着された第１の電子部品及び第２の電子部品と、を備える、接続構造体が提供される。 Moreover, in order to solve the said subject, according to another viewpoint of this invention, said 1st electronic component and 2nd electronic component which were adhere | attached via said adhesive composition with said adhesive composition A connection structure is provided.
また、上記課題を解決するために、本発明の別の観点によれば、上記の接着剤組成物を第１の電子部品と、第２の電子部品との間に設け、前記第１の電子部品又は前記第２の電子部品の側から加圧することで、前記第１の電子部品及び前記第２の電子部品を接続する、接続構造体の製造方法が提供される。 In order to solve the above problem, according to another aspect of the present invention, the adhesive composition is provided between a first electronic component and a second electronic component, and the first electronic component is provided. A method for manufacturing a connection structure is provided in which the first electronic component and the second electronic component are connected by applying pressure from the component or the second electronic component.
また、上記課題を解決するために、本発明の別の観点によれば、導電粒子をさらに含む上記の接着剤組成物と、前記接着剤組成物を介して接着された第１の電子部品及び第２の電子部品と、を備え、前記第１の電子部品が有する端子、及び前記第２の電子部品が有する端子は、前記導電粒子を挟持することで導電接続される、接続構造体が提供される。 In order to solve the above problems, according to another aspect of the present invention, the adhesive composition further including conductive particles, the first electronic component bonded via the adhesive composition, and A connection structure provided with a second electronic component, wherein the terminal included in the first electronic component and the terminal included in the second electronic component are conductively connected by sandwiching the conductive particles. Is done.
さらに、上記課題を解決するために、本発明の別の観点によれば、導電粒子をさらに含む上記の接着剤組成物を第１の電子部品と、第２の電子部品との間に設け、前記第１の電子部品又は前記第２の電子部品の側から加圧することで、前記第１の電子部品及び前記第２の電子部品を導電接続する、接続構造体の製造方法が提供される。 Furthermore, in order to solve the above problems, according to another aspect of the present invention, the adhesive composition further including conductive particles is provided between the first electronic component and the second electronic component, A method for manufacturing a connection structure is provided in which the first electronic component and the second electronic component are conductively connected by applying pressure from the first electronic component or the second electronic component.
上記構成により、膜形成樹脂又はアクリレート系化合物が有するカルボキシ基と、カルボジイミド系化合物とを反応させることによって、接着剤組成物の内部で分子間架橋を促すことが可能である。 With the above configuration, intermolecular crosslinking can be promoted inside the adhesive composition by reacting the carboxy group of the film-forming resin or the acrylate compound with the carbodiimide compound.
以上説明したように本発明によれば、より高い接着信頼性を有する接着剤組成物及び接続構造体を提供することができる。 As described above, according to the present invention, an adhesive composition and a connection structure having higher adhesion reliability can be provided.
以下に添付図面を参照しながら、本発明の好適な実施の形態について詳細に説明する。なお、本明細書及び図面において、実質的に同一の機能構成を有する構成要素については、同一の符号を付することにより重複説明を省略する。 Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.
＜１．接着剤組成物の構成＞
まず、本発明の一実施形態に係る接着剤組成物の構成について説明する。本実施形態に係る接着剤組成物は、膜形成樹脂と、アクリレート系化合物と、重合開始剤と、カルボジイミド系化合物と、を含む。
<1. Configuration of Adhesive Composition>
First, the structure of the adhesive composition which concerns on one Embodiment of this invention is demonstrated. The adhesive composition according to the present embodiment includes a film-forming resin, an acrylate compound, a polymerization initiator, and a carbodiimide compound.
本実施形態では、膜形成樹脂又はアクリレート系化合物の少なくとも１つ以上は、カルボキシ基を有する。これらの化合物が有するカルボキシ基は、カルボジイミド系化合物と反応することで、接着剤組成物の内部により多くの分子間架橋を形成することができる。これにより、本実施形態に係る接着剤組成物は、より高い接着信頼性を実現することができる。 In this embodiment, at least one or more of the film-forming resin or the acrylate compound has a carboxy group. The carboxy group which these compounds have can react with a carbodiimide type compound, and can form many intermolecular bridge | crosslinks inside an adhesive composition. Thereby, the adhesive composition which concerns on this embodiment can implement | achieve higher adhesion reliability.
膜形成樹脂は、接着剤組成物に成膜性を付与する。これにより、膜形成樹脂は、接着剤組成物の塗布性又はフィルム形成性を向上させ、かつ接着剤組成物の全体での凝集力を高めることができる。具体的には、膜形成樹脂は、１００００以上の平均分子量を有する有機樹脂であってもよい。膜形成樹脂は、塗布性又はフィルム形成性等を向上させる観点からは、１００００以上８００００以上の平均分子量を有する有機樹脂であることが好ましい。 The film-forming resin imparts film formability to the adhesive composition. Thereby, film formation resin can improve the applicability | paintability or film formation property of adhesive composition, and can raise the cohesion force in the whole adhesive composition. Specifically, the film-forming resin may be an organic resin having an average molecular weight of 10,000 or more. The film-forming resin is preferably an organic resin having an average molecular weight of 10,000 or more and 80000 or more from the viewpoint of improving applicability or film-forming property.
例えば、膜形成樹脂は、フェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、アクリル樹脂、ポリイミド樹脂、又はブチラール樹脂等を単独で、又は２種類以上組み合わせて用いてもよい。膜形成樹脂の含有量は、接着剤組成物の総質量に対して、例えば、４０質量％以上９０質量％以下であってもよく、好ましくは５０質量％以上８０質量％以下であってもよい。 For example, as the film-forming resin, a phenoxy resin, a polyester resin, a polyurethane resin, a polyester urethane resin, an acrylic resin, a polyimide resin, a butyral resin, or the like may be used alone or in combination of two or more. The content of the film-forming resin may be, for example, 40% by mass to 90% by mass, and preferably 50% by mass to 80% by mass with respect to the total mass of the adhesive composition. .
なお、上述したように、膜形成樹脂は、カルボキシ基を有し得る。このような膜形成樹脂としては、カルボキシ基を含むエステル結合又はウレタン結合等を主鎖に有するポリエステル樹脂、ポリウレタン樹脂又はポリエステルウレタン樹脂であってもよく、カルボキシ基を側鎖に有するアクリル樹脂を例示することができる。また、膜形成樹脂は、カルボジイミド系化合物との反応性をさらに高めるために、フェノール性ヒドロキシ基、エポキシ基、アミノ基又はヒドロキシ基をさらに有していてもよい。 As described above, the film-forming resin may have a carboxy group. Such a film-forming resin may be a polyester resin, a polyurethane resin or a polyester urethane resin having an ester bond or a urethane bond containing a carboxy group in the main chain, and an acrylic resin having a carboxy group in the side chain is exemplified. can do. The film-forming resin may further have a phenolic hydroxy group, an epoxy group, an amino group, or a hydroxy group in order to further increase the reactivity with the carbodiimide compound.
本実施形態では、後述するカルボジイミド系化合物との反応性を確保するために、膜形成樹脂は、ポリウレタン樹脂であることが好ましく、ポリエステルウレタン樹脂であることがより好ましい。ポリウレタン樹脂又はポリエステルウレタン樹脂は、主鎖のウレタン結合又はエステル結合にカルボキシ基を有する。これによれば、ポリウレタン樹脂又はポリエステルウレタン樹脂は、カルボジイミド系化合物との反応によって、より強固な分子間架橋を形成することができる。 In this embodiment, in order to ensure the reactivity with the carbodiimide type compound mentioned later, it is preferable that film forming resin is a polyurethane resin, and it is more preferable that it is a polyester urethane resin. The polyurethane resin or the polyester urethane resin has a carboxy group in the urethane bond or ester bond of the main chain. According to this, the polyurethane resin or the polyester urethane resin can form stronger intermolecular crosslinks by reaction with the carbodiimide-based compound.
特に、ポリエステルウレタン樹脂は、流動性が低いため、接着時に被接着物同士を低圧で押圧した場合にも十分な接着強度を確保することができる。このような場合、接着剤組成物は、薄いガラス基板又はプラスチック基板等の被接着物において、接着に起因する反りの発生を抑制することができる。 In particular, since the polyester urethane resin has low fluidity, sufficient adhesion strength can be ensured even when the adherends are pressed at a low pressure during bonding. In such a case, the adhesive composition can suppress the occurrence of warpage due to adhesion in an adherend such as a thin glass substrate or plastic substrate.
ここで、膜形成樹脂の酸価は、１ＫＯＨｍｇ／ｇ以上であることが好ましく、５ＫＯＨｍｇ／ｇ以上であることがより好ましい。酸価は、樹脂又は油脂等の高分子化合物１ｇ中に存在する遊離脂肪酸を中和するために必要な水酸化カリウムのｍｇ数を表すため、高分子化合物中に含まれるカルボン酸の量を表す指標となる。すなわち、膜形成樹脂では、酸価が高いほどカルボキシ基を多く有しているといえる。膜形成樹脂の酸価が１ＫＯＨｍｇ／ｇ以上である場合、カルボジイミド系化合物と反応し、架橋点となり得るカルボキシ基が膜形成樹脂に多く含まるため、接着剤組成物の接着信頼性をより向上させることができる。 Here, the acid value of the film-forming resin is preferably 1 KOH mg / g or more, and more preferably 5 KOH mg / g or more. The acid value represents the number of mg of potassium hydroxide required to neutralize free fatty acids present in 1 g of a polymer compound such as resin or oil, and therefore represents the amount of carboxylic acid contained in the polymer compound. It becomes an indicator. That is, it can be said that the film-forming resin has more carboxy groups as the acid value is higher. When the acid value of the film-forming resin is 1 KOHmg / g or more, the film-forming resin contains a large amount of carboxy groups that can react with the carbodiimide compound and become crosslinking points, thereby further improving the adhesion reliability of the adhesive composition. be able to.
ただし、膜形成樹脂の酸価が過剰に高い場合、遊離したカルボン酸が被接着物の金属部分等を腐食させる（マイグレーションともいう）可能性が生じる。したがって、膜形成樹脂の酸価は、５０ＫＯＨｍｇ／ｇ以下であることが好ましい。特に、金属端子同士を異方性導電接続する異方性接着剤として接着剤組成物を使用する場合、接続した金属端子の腐食を抑制するためには、膜形成樹脂の酸価は、上述した値以下とすることが好ましい。なお、膜形成樹脂の酸価が高い場合、接着剤組成物に酸化防止剤を添加することによって、接続した金属端子の腐食を抑制することも可能である。膜形成樹脂の酸価は、例えば、日本工業規格「ＪＩＳ Ｋ ００７０−１９９２ 化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法」に基づいて測定することができる。 However, when the acid value of the film-forming resin is excessively high, the liberated carboxylic acid may corrode the metal part or the like of the adherend (also referred to as migration). Accordingly, the acid value of the film-forming resin is preferably 50 KOH mg / g or less. In particular, when an adhesive composition is used as an anisotropic adhesive for anisotropically conductively connecting metal terminals, the acid value of the film-forming resin is as described above in order to suppress corrosion of the connected metal terminals. It is preferable to make it below the value. In addition, when the acid value of film forming resin is high, it is also possible to suppress corrosion of the connected metal terminal by adding an antioxidant to the adhesive composition. The acid value of the film-forming resin is measured based on, for example, Japanese Industrial Standards “JIS K 0070-1992 Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value, and Unsaponified Test Method for Chemical Products”. be able to.
アクリレート系化合物は、接着剤組成物に接着性を付与する。アクリレート系化合物は、接着時に硬化することで、被接着物同士を接着させる。具体的には、アクリレート系化合物は、ラジカル重合性を有する（メタ）アクリレート樹脂であってもよい。なお、（メタ）アクリレートとは、アクリル酸エステル（すなわち、アクリレート）、及びメタクリル酸エステル（すなわち、メタクリレート）を含むことを表す。（メタ）アクリレート樹脂は、低温でも反応性が高いため、接着剤組成物は、接着時の加熱温度が低い場合でも、確実に被接着物同士を接着することができる。これによれば、接着剤組成物は、熱によってダメージを受ける可能性がある被接着物であっても、問題なく接着することができる。アクリレート系化合物の含有量は、接着剤組成物の総質量に対して、例えば、５質量％以上４０質量％以下であってもよく、好ましくは１０質量％以上３０質量％以下であってもよい。 The acrylate compound imparts adhesiveness to the adhesive composition. The acrylate-based compound is cured at the time of bonding, thereby bonding objects to be bonded together. Specifically, the acrylate compound may be a (meth) acrylate resin having radical polymerizability. In addition, (meth) acrylate represents containing acrylate ester (namely, acrylate) and methacrylic acid ester (namely, methacrylate). Since the (meth) acrylate resin has high reactivity even at a low temperature, the adhesive composition can reliably adhere objects to be bonded even when the heating temperature at the time of bonding is low. According to this, even if it is a to-be-adhered object which may receive damage with a heat | fever, an adhesive composition can adhere | attach without a problem. The content of the acrylate compound may be, for example, 5% by mass to 40% by mass, and preferably 10% by mass to 30% by mass with respect to the total mass of the adhesive composition. .
アクリレート系化合物は、例えば、アクリレート残基又はメタクリレート残基を分子内に含む単官能又は多官能モノマー又はオリゴマーであってもよい。 The acrylate compound may be, for example, a monofunctional or polyfunctional monomer or oligomer containing an acrylate residue or a methacrylate residue in the molecule.
単官能の（メタ）アクリレートモノマーとしては、直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレートを例示することができる。例えば、アルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ｎ−へキシル（メタ）アクリレート、シクロヘキシルアクリレート、ｎ−ヘプチル（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、２−エチルヘキシル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ｎ−トリデシル（メタ）アクリレート、ｎ−テトラデシル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、又はｎ−ラウリル（メタ）アクリレート等を列挙することができる。 Examples of the monofunctional (meth) acrylate monomer include alkyl (meth) acrylates having a linear or branched alkyl group. For example, as alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) Acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate Rate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl ( A meth) acrylate, n-lauryl (meth) acrylate, etc. can be enumerated.
多官能の（メタ）アクリレートとしては、例えば、トリシクロデカンジメタノールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、ネオペンタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート若しくはポリプロピレングリコールジ（メタ）アクリレート等の２官能の（メタ）アクリレート、又はトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（アクリロイルオキシエチル）イソシアヌレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート若しくはジペンタエリスリトールヘキサ（メタ）アクリレート等の３官能以上の（メタ）アクリレートを列挙することができる。 Examples of the polyfunctional (meth) acrylate include tricyclodecane dimethanol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and neopentanediol. Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di ( Bifunctional (meth) acrylates such as (meth) acrylate, tripropylene glycol di (meth) acrylate or polypropylene glycol di (meth) acrylate, or trimethylolpropane tri (meth) acrylate, pentaerythritol Li (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate or dipentaerythritol hexa (meth) Trifunctional or higher functional (meth) acrylates such as acrylates can be listed.
なお、上述したように、アクリレート系化合物は、カルボキシ基を有し得る。アクリレート系化合物がカルボキシ基を有する場合、接着剤組成物では、カルボジイミド系化合物によって分子間架橋が促されるため、接着信頼性をより向上させることができる。また、アクリレート系化合物は、カルボジイミド系化合物との反応性をさらに高めるために、フェノール性ヒドロキシ基、エポキシ基、アミノ基又はヒドロキシ基をさらに有していてもよい。 As described above, the acrylate compound may have a carboxy group. When the acrylate compound has a carboxy group, in the adhesive composition, intermolecular crosslinking is promoted by the carbodiimide compound, so that the adhesion reliability can be further improved. The acrylate compound may further have a phenolic hydroxy group, an epoxy group, an amino group, or a hydroxy group in order to further increase the reactivity with the carbodiimide compound.
重合開始剤は、アクリレート系化合物の重合を開始させる化合物である。具体的には、重合開始剤は、外部からの刺激（光、熱又は圧力等）によってラジカルを発生させるラジカル系重合開始剤であってもよい。重合開始剤は、公知のラジカル系重合開始剤であってもよいが、例えば、過酸化物系ラジカル開始剤であってもよい。重合開始剤は、例えば、ベンゾイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチルパーオキシベンゾエート等のアルキルパーエステル類、１、１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン等のパーオキシケタール類を単独、又は２種類以上組み合わせて用いてもよい。重合開始剤の含有量は、接着剤組成物の総質量に対して、例えば、１質量％以上５０質量％以下であってもよく、好ましくは５質量％以上３０質量％以下であってもよい。 The polymerization initiator is a compound that initiates polymerization of the acrylate compound. Specifically, the polymerization initiator may be a radical polymerization initiator that generates radicals by external stimulation (light, heat, pressure, or the like). The polymerization initiator may be a known radical polymerization initiator, but may be, for example, a peroxide radical initiator. Examples of the polymerization initiator include diacyl peroxides such as benzoyl peroxide, alkyl peresters such as t-hexyl peroxypivalate and t-butyl peroxybenzoate, and 1,1-di (t-butylperoxy). Peroxyketals such as cyclohexane may be used alone or in combination of two or more. The content of the polymerization initiator may be, for example, 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass with respect to the total mass of the adhesive composition. .
カルボジイミド系化合物は、化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基を含む化合物である。化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基は、官能基内での分極が大きい。そのため、カルボジイミド系化合物は、接着剤組成物に含まれることによって以下のような効果を奏することが期待される。 A carbodiimide compound is a compound containing a functional group represented by a chemical formula (—N═C═N—). The functional group represented by the chemical formula (—N═C═N—) has a large polarization within the functional group. Therefore, it is expected that the carbodiimide-based compound has the following effects by being included in the adhesive composition.
例えば、カルボジイミド系化合物は、被接着物の極性表面との静電気的な相互作用によって、接着剤組成物の接着強度を向上させることが期待される。また、カルボジイミド系化合物は、水素イオン又は水酸化物イオン等の遊離イオンを捕捉することによって、膜形成樹脂の加水分解を抑制したり、被接着物の表面の腐食を防止したりすることが期待される。さらに、酸捕捉剤として機能するカルボジイミド系化合物を接着剤組成物に添加した場合、酸捕捉剤として金属酸化物又はハイドロタルサイト等の無機化合物を接着剤組成物に添加しなくともよくなる。これによれば、接着剤組成物を異方性接着剤として用いる場合、金属酸化物又はハイドロタルサイト等の無機化合物に起因して、接続端子間で短絡が発生することを抑制することが期待される。 For example, the carbodiimide compound is expected to improve the adhesive strength of the adhesive composition by electrostatic interaction with the polar surface of the adherend. In addition, carbodiimide compounds are expected to suppress hydrolysis of the film-forming resin and prevent corrosion of the surface of the adherend by capturing free ions such as hydrogen ions or hydroxide ions. Is done. Furthermore, when a carbodiimide-based compound that functions as an acid scavenger is added to the adhesive composition, it is not necessary to add an inorganic compound such as a metal oxide or hydrotalcite to the adhesive composition as the acid scavenger. According to this, when the adhesive composition is used as an anisotropic adhesive, it is expected to suppress occurrence of a short circuit between the connection terminals due to an inorganic compound such as a metal oxide or hydrotalcite. Is done.
特に、膜形成樹脂がポリウレタン樹脂又はポリエステルウレタン樹脂である場合、膜形成樹脂の主鎖に含まれるウレタン結合又はエステル結合は、酸を触媒として加水分解されやすい。そのため、酸捕捉剤として機能するカルボジイミド系化合物を接着剤組成物に含有させることにより、ポリウレタン樹脂又はポリエステルウレタン樹脂における加水分解反応を効果的に抑制することができる。また、カルボジイミド系化合物は、ポリウレタン樹脂又はポリエステルウレタン樹脂が有するカルボキシ基と反応して分子間架橋を促すことで、接着剤組成物の接着強度を向上させることができる。 In particular, when the film-forming resin is a polyurethane resin or a polyester urethane resin, the urethane bond or ester bond contained in the main chain of the film-forming resin is easily hydrolyzed using an acid as a catalyst. Therefore, the hydrolysis reaction in a polyurethane resin or a polyester urethane resin can be effectively suppressed by including in the adhesive composition a carbodiimide compound that functions as an acid scavenger. Moreover, the carbodiimide-type compound can improve the adhesive strength of adhesive composition by reacting with the carboxy group which a polyurethane resin or a polyester urethane resin has, and promoting intermolecular crosslinking.
なお、上述したカルボジイミド系化合物にて促される分子間架橋反応は、被接着物の接着時に生じず、接着後の高温高湿環境下で生じる。したがって、接着剤組成物では、長期経過後でも接着強度が維持又は向上するため、より高い接着信頼性を実現することができる。すなわち、接着剤組成物は、高温高湿等の過酷な環境下でも十分な接着信頼性を維持することができるため、高い耐候性を有することができる。 In addition, the intermolecular crosslinking reaction promoted by the carbodiimide-based compound described above does not occur when the adherend is adhered, but occurs in a high-temperature and high-humidity environment after adhesion. Therefore, in the adhesive composition, the adhesive strength is maintained or improved even after a long period of time, so that higher adhesion reliability can be realized. That is, since the adhesive composition can maintain sufficient adhesion reliability even in a harsh environment such as high temperature and high humidity, it can have high weather resistance.
なお、上述した効果は、カルボジイミド系化合物が化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基を含むことによる効果である。したがって、本明細書にて説明するカルボジイミド系化合物は、カルボジイミドを出発物質とする変性体、反応生成物又は誘導体などのような化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基が分子内に有しない化合物を含まない。 In addition, the effect mentioned above is an effect by the carbodiimide type compound containing the functional group represented by chemical formula (-N = C = N-). Therefore, in the carbodiimide compound described in this specification, a functional group represented by a chemical formula (—N═C═N—) such as a modified body, a reaction product, or a derivative starting from carbodiimide is a molecule. Does not contain compounds that do not have it inside.
なお、化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基が分子内に極めて少ない場合、例えば、化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基が不可避的に混入する場合は、化学式（−Ｎ＝Ｃ＝Ｎ−）で表される官能基が含まれないと解釈してもよい。 In addition, when the functional group represented by the chemical formula (-N = C = N-) is extremely small in the molecule, for example, the functional group represented by the chemical formula (-N = C = N-) is inevitably mixed. In the case, it may be interpreted that the functional group represented by the chemical formula (—N═C═N—) is not included.
このようなカルボジイミド系化合物は、モノマー、オリゴマー又はポリマーであってもよい。例えば、カルボジイミド系化合物として、多価カルボジイミド（例えば、ポリカルボジイミド）又はカルボジイミド変性イソシアネートなどを好ましく用いることができる。カルボジイミド系化合物は、比較的分子量が大きいポリマーであることが好ましい。 Such carbodiimide compounds may be monomers, oligomers or polymers. For example, as the carbodiimide compound, polyvalent carbodiimide (for example, polycarbodiimide) or carbodiimide-modified isocyanate can be preferably used. The carbodiimide compound is preferably a polymer having a relatively large molecular weight.
カルボジイミド系化合物は、カルボキシ基を有する膜形成樹脂又はアクリレート系化合物の総質量に対して、０．１質量％以上１５０質量％以下で接着剤組成物に含まれる。カルボジイミド系化合物の含有量がカルボキシ基を有する化合物の総質量に対して０．１質量％未満である場合、接着剤組成物の接着信頼性を向上させる効果が得られない。したがって、カルボジイミド系化合物の含有量の下限は、カルボキシ基を有する化合物の総質量に対して０．１質量％であり、好ましくは５質量％である。一方、カルボジイミド系化合物の含有量がカルボキシ基を有する化合物の総質量に対して１５０質量％超である場合、接着剤組成物中にカルボジイミド系化合物を均一に分散させることが困難になる。したがって、カルボジイミド系化合物の含有量の上限は、カルボキシ基を有する化合物の総質量に対して１５０質量％であり、好ましくは３０質量％である。 The carbodiimide compound is contained in the adhesive composition in an amount of 0.1% by mass or more and 150% by mass or less based on the total mass of the film-forming resin or acrylate compound having a carboxy group. When content of a carbodiimide type compound is less than 0.1 mass% with respect to the total mass of the compound which has a carboxy group, the effect which improves the adhesive reliability of adhesive composition is not acquired. Therefore, the lower limit of the content of the carbodiimide compound is 0.1% by mass, preferably 5% by mass with respect to the total mass of the compound having a carboxy group. On the other hand, when the content of the carbodiimide compound is more than 150% by mass with respect to the total mass of the compound having a carboxy group, it becomes difficult to uniformly disperse the carbodiimide compound in the adhesive composition. Therefore, the upper limit of the content of the carbodiimide-based compound is 150% by mass, preferably 30% by mass, based on the total mass of the compound having a carboxy group.
以上にて説明したように、本実施形態に係る接着剤組成物は、カルボジイミド系化合物を含むことによって、接着信頼性を向上させることができる。また、本実施形態に係る接着剤組成物は、異方性接着剤として用いられる場合、さらに、被接着物の耐腐食性及び導電接続の信頼性をも向上させることができる。 As explained above, the adhesive composition according to the present embodiment can improve adhesion reliability by including a carbodiimide compound. Moreover, when the adhesive composition according to the present embodiment is used as an anisotropic adhesive, it can further improve the corrosion resistance of the adherend and the reliability of the conductive connection.
なお、接着剤組成物は、上述した化合物以外に、必要に応じて、シランカップリング剤、無機フィラー、着色剤又は酸化防止剤等の添加剤をさらに含んでもよい。さらに、接着剤剤組成物は、上述した各化合物に加えて、又は替えて、特開２０１０−２３２１９１又は特開２０１０−２４２１０１に記載された一般的な化合物を含有していてもよい。 In addition, the adhesive composition may further include additives such as a silane coupling agent, an inorganic filler, a colorant, or an antioxidant, as necessary, in addition to the above-described compounds. Furthermore, the adhesive composition may contain general compounds described in JP2010-232191A or JP2010-242101 in addition to or in place of the above-described compounds.
＜２．接着剤組成物の適用例＞
（２．１．第１の適用例）
次に、図１及び図２を参照して、本実施形態に係る接着剤組成物の第１の適用例について説明する。図１は、接着剤組成物の第１の適用例を説明する模式図であり、図２は、接着剤組成物の第１の適用例による接着を説明する模式図である。
<2. Application example of adhesive composition>
(2.1. First application example)
Next, with reference to FIG.1 and FIG.2, the 1st application example of the adhesive composition which concerns on this embodiment is demonstrated. FIG. 1 is a schematic diagram illustrating a first application example of the adhesive composition, and FIG. 2 is a schematic diagram illustrating adhesion according to the first application example of the adhesive composition.
図１に示すように、接着剤組成物の第１の適用例は、ベースフィルム１１０の上に接着剤組成物１０１を含む接着層１００が形成された接着フィルム１１である。接着フィルム１１は、ベースフィルム１１０と、接着層１００とを備え、例えば、リール部材等に巻き取られたロール形態にて保管される。
As shown in FIG. 1, the first application example of the adhesive composition is an
ベースフィルム１１０は、接着層１００を支持する樹脂フィルムであり、例えば、ポリエチレンテレフタラート（ＰｏｌｙＥｔｈｙｌｅｎｅ Ｔｅｒｅｐｈｔｈａｌａｔｅ：ＰＥＴ）にて構成される。接着層１００は、本実施形態に係る接着剤組成物１０１を含む層であり、ベースフィルム１１０の一面にフィルム状に設けられる。
The
第１の適用例では、図２に示すように、接着剤組成物１０１を含む接着層１００は、ベースフィルム１１０から剥離されて被接着物２０、３０に貼付され、加熱及び押圧されることで被接着物２０、３０を接着する。被接着物２０、３０は、例えば、ガラス基板、リジット基板、プラスチック基板若しくはセラミック基板などの各種基板、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ Ｃｉｒｃｕｉｔ）チップなどの半導体素子、ＦＰＣ（Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔ）又はＩＣ（Ｉｎｔｅｇｒａｔｅｄ Ｃｉｒｃｕｉｔ）チップ、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）テープ若しくは機能性モジュールなどの電子部品などであってもよい。
In the first application example, as shown in FIG. 2, the
接着剤組成物の第１の適用例によれば、被接着物同士の間で信頼性の高い接着を行うことができる。また、他の使用例として、接着剤組成物は、構造体に設けられた空間の充填に用いることができる。 According to the first application example of the adhesive composition, it is possible to perform highly reliable bonding between objects to be bonded. As another use example, the adhesive composition can be used for filling a space provided in the structure.
（２．２．第２の適用例）
続いて、図３及び図４を参照して、本実施形態に係る接着剤組成物の第２の適用例について説明する。図３は、接着剤組成物の第２の適用例を説明する模式図であり、図４は、接着剤組成物の第２の適用例による接着を説明する模式図である。
(2.2. Second application example)
Subsequently, a second application example of the adhesive composition according to this embodiment will be described with reference to FIGS. 3 and 4. FIG. 3 is a schematic diagram illustrating a second application example of the adhesive composition, and FIG. 4 is a schematic diagram illustrating adhesion according to the second application example of the adhesive composition.
図３に示すように、接着剤組成物の第２の適用例は、ベースフィルム１１０の上に接着剤組成物１０１及び導電粒子１０２を含む接着層１００が形成された異方性導電接続フィルム１２である。異方性導電接続フィルム１２は、ベースフィルム１１０と、接着層１００とを備え、例えば、リール部材等に巻き取られたロール形態にて保管される。なお、第２の適用例についての説明は、本発明の技術的範囲から接着剤組成物１０１が導電粒子１０２を含まない様態、又は接着剤組成物１０１が接着層１００として形成されていない様態などを除外するものではない。
As shown in FIG. 3, the second application example of the adhesive composition is an anisotropic
ベースフィルム１１０は、接着層１００を支持する樹脂フィルムであり、例えば、ポリエチレンテレフタラート（ＰｏｌｙＥｔｈｙｌｅｎｅ Ｔｅｒｅｐｈｔｈａｌａｔｅ：ＰＥＴ）にて構成される。接着層１００は、本実施形態に係る接着剤組成物１０１及び導電粒子１０２を含む層であり、ベースフィルム１１０の一面にフィルム状に設けられる。
The
導電粒子１０２は、例えば、ニッケル、鉄、銅、アルミニウム、スズ、鉛、クロム、コバルト、銀若しくは金等の金属からなる粒子、又はこれらの金属合金からなる粒子であってもよい。または、導電粒子１０２は、樹脂粒子の表面に前述した金属又は合金を被覆した粒子であってもよい。さらには、導電粒子１０２は、前述した金属粒子、合金粒子又は金属被覆粒子の表面に絶縁薄膜を被覆した粒子であってもよい。導電粒子１０２の平均粒径は、被接着物同士の導通信頼性を確保する観点から、例えば、１μｍ以上３０μｍ以下であってもよく、好ましくは２μｍ以上１０μｍ以下であってもよい。導電粒子１０２の含有量は、被接着物同士の導通信頼性及び絶縁信頼性を確保する観点から、例えば、接着層１００の総質量に対して２質量％以上５０質量％以下であってもよく、好ましくは、３質量％以上２０質量％以下であってもよい。
The
第２の適用例では、図４に示すように、接着剤組成物１０１及び導電粒子１０２を含む接着層１００は、ベースフィルム１１０から剥離されて、接着面に端子２１０、３１０が設けられた被接着物２０、３０に貼付される。なお、端子２１０、３１０は、それぞれ被接着物２０、３０に形成された回路に接続される。ここで、接着層１００は、加熱及び押圧されることで被接着物２０、３０を接着し、導電粒子１０２は、被接着物２０、３０の接着面に設けられた端子２１０、３１０に挟持されることで、端子２１０、３１０を互いに電気的に接続する。
In the second application example, as shown in FIG. 4, the
被接着物２０、３０は、例えば、ガラス基板、リジット基板、プラスチック基板若しくはセラミック基板などの各種回路基板、ＦＰＣ（Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔ）又はＩＣチップなどの半導体素子、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）テープ若しくは機能性モジュールなどの電子部品などであってもよい。
The
接着剤組成物の第２の適用例によれば、被接着物同士の間で信頼性の高い接着を行うと共に、被接着物に形成された回路同士を電気的に接続することができる。 According to the second application example of the adhesive composition, it is possible to perform highly reliable adhesion between adherends and to electrically connect circuits formed on the adherends.
以下では、実施例を参照しながら、本実施形態に係る接着剤組成物及び接続構造体の製造方法について、より詳細に説明する。なお、以下に示す実施例は、本実施形態に係る接着剤組成物及び接続構造体の製造方法の実施可能性および効果を示すための一例であり、本発明が以下の実施例に限定されるものではない。 Below, the manufacturing method of the adhesive composition which concerns on this embodiment, and a connection structure is demonstrated in detail, referring an Example. In addition, the Example shown below is an example for showing the feasibility and the effect of the manufacturing method of the adhesive composition and the connection structure according to the present embodiment, and the present invention is limited to the following example. It is not a thing.
（接着剤組成物の製造）
下記表１にて示す材料を混合し、接着剤組成物を調製した。その後、調整した接着剤組成物に導電粒子（平均粒子径４μｍ、積水化学工業社製ＡＵＬ７０４）を分散させた。導電粒子を分散させた接着剤組成物は、乾燥後の接着剤組成物の平均膜厚が１０μｍになるように、ＰＥＴフィルムに塗布し、乾燥させた。これにより、異方性接着剤及び異方性導電フィルムとして機能する接着剤組成物および接着フィルムを製造した。例えば、乾燥後の接着剤組成物の平均膜厚が１０μｍである場合、導電粒子は、個数密度が８０００個／ｍｍ２となるように調整されて、接着剤組成物に配合されてもよい。導電粒子の個数密度は、２００μｍ×２００μｍ四方の領域を任意に抜き取った１０点における導電粒子の個数密度を金属顕微鏡にて観察し、平均値を算出することで求めた。
(Manufacture of adhesive composition)
The materials shown in Table 1 below were mixed to prepare an adhesive composition. Thereafter, conductive particles (average particle diameter 4 μm, AUL 704 manufactured by Sekisui Chemical Co., Ltd.) were dispersed in the adjusted adhesive composition. The adhesive composition in which the conductive particles were dispersed was applied to a PET film and dried so that the average film thickness of the adhesive composition after drying was 10 μm. Thereby, the adhesive composition and adhesive film which function as an anisotropic adhesive agent and an anisotropic conductive film were manufactured. For example, when the average film thickness of the adhesive composition after drying is 10 μm, the conductive particles may be adjusted to have a number density of 8000 / mm 2 and blended in the adhesive composition. The number density of the conductive particles was obtained by observing the number density of the conductive particles at 10 points arbitrarily extracted from a 200 μm × 200 μm square area with a metal microscope and calculating an average value.
表１において、「ＵＲ８２００」（東洋紡績社製）、「ＵＲ１７００」（東洋紡績社製）及び「ＵＲ３５００」（東洋紡績社製）はカルボキシ基を有する膜形成樹脂に相当する。「ＵＲ８２００」の酸価は、０．５ＫＯＨｍｇ／ｇ未満であり、「ＵＲ１７００」の酸価は、２６ＫＯＨｍｇ／ｇであり、「ＵＲ３５００」の酸価は、３５ＫＯＨｍｇ／ｇである。「ＥＢ−６００」（ダイセル・サイテック社製）はカルボキシ基を有しないアクリレート系化合物に相当し、「パーヘキサＣ」（日油社製）は重合開始剤に相当し、「Ｓｔａｂａｘｏｌ（登録商標）Ｐ」（ＲｈｅｉｎＣｈｅｍｉｅ社製）は、カルボジイミド系化合物に相当する。「ＫＢＭ−５０３」（信越化学工業社製）は、シランカップリング剤である。 In Table 1, “UR8200” (manufactured by Toyobo Co., Ltd.), “UR1700” (manufactured by Toyobo Co., Ltd.) and “UR3500” (manufactured by Toyobo Co., Ltd.) correspond to a film-forming resin having a carboxy group. The acid value of “UR8200” is less than 0.5 KOHmg / g, the acid value of “UR1700” is 26 KOHmg / g, and the acid value of “UR3500” is 35 KOHmg / g. “EB-600” (manufactured by Daicel Cytec) corresponds to an acrylate compound having no carboxy group, “Perhexa C” (manufactured by NOF Corporation) corresponds to a polymerization initiator, and “Stabaxol® P” "(Rhein Chemie) corresponds to a carbodiimide compound. “KBM-503” (manufactured by Shin-Etsu Chemical Co., Ltd.) is a silane coupling agent.
なお、表１で示した割合の単位は、「質量部」である。さらに、表１では、カルボキシ基を含有する樹脂（「ＵＲ８２００」、「ＵＲ１７００」、及び「ＵＲ３５００」）に対するカルボジイミド系化合物（Ｓｔａｂａｘｏｌ Ｐ）の質量割合も示した。 In addition, the unit of the ratio shown in Table 1 is “part by mass”. Furthermore, in Table 1, the mass ratio of the carbodiimide type compound (Stabaxol P) with respect to resin ("UR8200", "UR1700", and "UR3500") containing a carboxy group was also shown.
（接続構造体の製造）
続いて、上記製造した接着剤組成物を用いて接続構造体を製造した。具体的には、８μｍ厚みのＣｕで形成され、Ｓｎめっきを施した端子が５０μｍピッチで配置されたＦＰＣ（Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔ）（厚み３８μｍ）を用意した。また、表面の全域に亘って酸化インジウムスズ（ＩＴＯ）がコーティングされたガラス基板（厚み０．７ｍｍ）を用意した。
(Manufacture of connection structure)
Subsequently, a connection structure was manufactured using the manufactured adhesive composition. Specifically, an FPC (Flexible Printed Circuit) (thickness: 38 μm) formed of Cu having a thickness of 8 μm and terminals plated with Sn arranged at a pitch of 50 μm was prepared. A glass substrate (thickness 0.7 mm) coated with indium tin oxide (ITO) over the entire surface was prepared.
上記で製造した接着剤組成物を１．５ｍｍ幅のスリット状に裁断し、ＩＴＯコーティングガラス基板に貼り付けた。その後、接着剤組成物の上に、ＩＴＯコーティングガラス基板と端子が対向するようにＦＰＣを載置し、仮固定した。続いて、１００μｍ厚のテフロン（登録商標）材を緩衝材として用いて、仮固定したＩＴＯコーティングガラス基板、接着剤組成物及びＦＰＣを幅１．５ｍｍの圧着ツールで本圧着した。これにより、接続構造体を製造した。なお、本圧着の条件は、１８０℃かつ３．５ＭＰａで６秒間とし、圧着ステージの温度は４０℃とした。 The adhesive composition produced above was cut into a 1.5 mm wide slit and attached to an ITO coated glass substrate. Then, FPC was mounted on the adhesive composition so that the ITO coated glass substrate and the terminal faced each other, and temporarily fixed. Subsequently, using a Teflon (registered trademark) material having a thickness of 100 μm as a buffer material, the temporarily fixed ITO coated glass substrate, the adhesive composition, and the FPC were subjected to main pressure bonding with a pressure bonding tool having a width of 1.5 mm. Thereby, the connection structure was manufactured. The conditions for the main pressure bonding were 180 ° C. and 3.5 MPa for 6 seconds, and the temperature of the pressure bonding stage was 40 ° C.
（評価方法）
以上で製造した接続構造体について、導通抵抗、接着強度及び圧痕信頼性を評価した。なお、導通抵抗及び接着強度は、初期及び信頼性試験後でそれぞれ評価した。信頼性試験は、環境試験条件として温度８５℃／湿度８５％ＲＨを用い、接続構造体を前述の高温高湿下で５００時間放置することで行った。なお、信頼性試験には、環境試験機（恒温恒湿器、エスペック社製ＰＲシリーズ）を用いた。
(Evaluation methods)
About the connection structure manufactured above, conduction resistance, adhesive strength, and indentation reliability were evaluated. The conduction resistance and the adhesive strength were evaluated at the initial stage and after the reliability test, respectively. The reliability test was performed by using a temperature of 85 ° C./humidity of 85% RH as environmental test conditions and leaving the connection structure for 500 hours under the above-described high temperature and high humidity. For the reliability test, an environmental testing machine (constant temperature and humidity chamber, PR series manufactured by Espec) was used.
導通抵抗は、デジタルマルチメータ（横河電機社製デジタルマルチメータ７５５５、）を用いて測定した。具体的には、四端子法にて電流を１ｍＡ流した時に測定された接続抵抗を導通抵抗とした。具体的には、導通抵抗が２Ω未満であるものをＡ（とても好ましい）、２Ω以上４Ω以下であるものをＢ（問題なし）、４Ω超であるものをＣ（ＮＧ）として評価した。 The conduction resistance was measured using a digital multimeter (Yokogawa Digital Multimeter 7555). Specifically, the connection resistance measured when a current of 1 mA was passed by the four-terminal method was defined as a conduction resistance. Specifically, the case where the conduction resistance was less than 2Ω was evaluated as A (very preferable), the case where the resistance was 2Ω or more and 4Ω or less was B (no problem), and the case where the conduction resistance was more than 4Ω was evaluated as C (NG).
接着強度は、引張試験機（ＡＭＤ社製ＲＴＣ１２０１）を用いて測定した。具体的には、接着したＦＰＣを、ＩＴＯコーティングガラス基板に対して９０°の角度で５０ｍｍ／秒の速度で引き上げ、ＦＰＣが剥離した際に測定された引張強度を接着強度とした。具体的には、接着強度が８Ｎ／ｃｍ超であるものをＡ（とても好ましい）、５Ｎ／ｃｍ以上８Ｎ／ｃｍ以下であるものをＢ（問題なし）、５Ｎ／ｃｍ未満であるものをＣ（ＮＧ）として評価した。 The adhesive strength was measured using a tensile tester (AMC RTC1201). Specifically, the adhered FPC was pulled up at an angle of 90 ° with respect to the ITO-coated glass substrate at a speed of 50 mm / second, and the tensile strength measured when the FPC peeled was defined as the adhesive strength. Specifically, those having an adhesive strength of more than 8 N / cm are A (very preferable), those having an adhesive strength of 5 N / cm or more and 8 N / cm or less are B (no problem), and those having an adhesion strength of less than 5 N / cm are C ( NG).
圧痕信頼性は、微分干渉顕微鏡（オリンパス社製ＭＸ５１）を用いて、接続構造体を観察することで評価した。具体的には、比較例１に係る接続構造体で観察された圧痕を基準として、圧痕がより明りょうに観察される場合をＡ、圧痕が同等に観察される場合をＢ、圧痕が明りょうに観察されない場合をＣとして評価した。なお、Ａの方がＣよりも評価が良好であることを示す。 Indentation reliability was evaluated by observing the connection structure using a differential interference microscope (MX51 manufactured by Olympus Corporation). Specifically, based on the indentation observed in the connection structure according to Comparative Example 1, A is a case where the indentation is observed more clearly, B is a case where the indentation is observed equally, and the indentation is clear. The case where it was not observed was evaluated as C. In addition, A shows that evaluation is better than C.
総合判定は、導通抵抗及び接着強度の初期及び信頼性試験後の評価結果、並びに圧痕信頼性を総合的に判断することで評価した。Ａの方がＣよりも評価が良好であることを示す。なお、接続構造体の実用上、Ｂ以上の評価であることが好ましい。 The comprehensive judgment was evaluated by comprehensively judging the evaluation results after the initial and reliability tests of the conduction resistance and the adhesive strength, and the indentation reliability. A shows that evaluation is better than C. In addition, it is preferable that the evaluation is B or more in practical use of the connection structure.
以上の結果を下記の表２に示す。比較例２及び４は、接着剤組成物がフィルム化できなかったため、導通抵抗及び接着強度は評価していない。 The above results are shown in Table 2 below. In Comparative Examples 2 and 4, since the adhesive composition could not be formed into a film, conduction resistance and adhesive strength were not evaluated.
表２の結果を参照すると、実施例１〜９に係る接続構造体は、比較例１〜４と比較して、信頼性試験後も導通抵抗が大きく増加しておらず、かつ接着強度も大きく低下していないことがわかる。 Referring to the results in Table 2, the connection structures according to Examples 1 to 9 do not have a large increase in conduction resistance after the reliability test and have a large adhesive strength as compared with Comparative Examples 1 to 4. It turns out that it has not fallen.
また、カルボキシ基を有する膜形成樹脂の酸価がより高い実施例７〜９は、実施例１〜６と比較して、信頼性試験後の接着強度の評価が高いことがわかる。したがって、実施例７〜９は、実施例１〜６と比較して、より耐候性が高いことがわかる。 Moreover, it turns out that Example 7-9 with higher acid value of film formation resin which has a carboxy group has high evaluation of the adhesive strength after a reliability test compared with Examples 1-6. Therefore, it turns out that Examples 7-9 have higher weather resistance compared with Examples 1-6.
以上の結果から、本実施形態に係る接着剤組成物は、信頼性試験後も高い接着強度を維持することが可能であるため、高い接着信頼性を有することがわかる。 From the above results, it can be seen that the adhesive composition according to the present embodiment can maintain high adhesion strength even after the reliability test, and thus has high adhesion reliability.
以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。 The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
１１ 接着フィルム
１２ 異方性導電接続フィルム
２０、３０ 被接着物
１００ 接着層
１０１ 接着剤組成物
１０２ 導電粒子
１１０ ベースフィルム
２１０、３１０ 端子
DESCRIPTION OF
Claims (13)
アクリレート系化合物と、
重合開始剤と、
カルボジイミド系化合物と、
を含有し、
前記膜形成樹脂又は前記アクリレート系化合物の少なくとも１つ以上は、カルボキシ基を有する化合物であり、
前記カルボジイミド系化合物の含有量は、前記カルボキシ基を有する化合物の総質量に対して、０．１質量％以上１５０質量％以下である、接着剤組成物。 A film-forming resin;
An acrylate compound;
A polymerization initiator;
A carbodiimide compound,
Containing
At least one or more of the film-forming resin or the acrylate compound is a compound having a carboxy group,
Content of the said carbodiimide type compound is an adhesive composition which is 0.1 to 150 mass% with respect to the total mass of the compound which has the said carboxy group.
前記接着剤組成物を介して接着された第１の電子部品及び第２の電子部品と、
を備える、接続構造体。 The adhesive composition according to any one of claims 1 to 8,
A first electronic component and a second electronic component bonded via the adhesive composition;
A connection structure comprising:
前記接着剤組成物を介して接着された第１の電子部品及び第２の電子部品と、
を備え、
前記第１の電子部品が有する端子、及び前記第２の電子部品が有する端子は、前記導電粒子を挟持することで導電接続される、接続構造体。 An adhesive composition according to claim 9;
A first electronic component and a second electronic component bonded via the adhesive composition;
With
A connection structure in which a terminal included in the first electronic component and a terminal included in the second electronic component are conductively connected by sandwiching the conductive particles.
By providing the adhesive composition according to claim 9 between the first electronic component and the second electronic component, and pressurizing from the side of the first electronic component or the second electronic component, A method for manufacturing a connection structure, wherein the first electronic component and the second electronic component are conductively connected.
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| JP2018070659A JP7264598B2 (en) | 2018-04-02 | 2018-04-02 | Adhesive composition and connecting structure |
| PCT/JP2019/007517 WO2019193880A1 (en) | 2018-04-02 | 2019-02-27 | Adhesive composition, connection structure, and manufacturing method of connection structure |
| KR1020207026558A KR102522875B1 (en) | 2018-04-02 | 2019-02-27 | Adhesive composition, bonded structure, and manufacturing method of bonded structure |
| CN201980020386.3A CN111868198B (en) | 2018-04-02 | 2019-02-27 | Adhesive composition, connection structure, and method for producing connection structure |
| TW108110926A TW201943825A (en) | 2018-04-02 | 2019-03-28 | Adhesive composition, connection structure, and manufacturing method of connection structure |
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| JP2014201701A (en) * | 2013-04-08 | 2014-10-27 | 東洋インキＳｃホールディングス株式会社 | Resin composition, active energy ray-polymerizable adhesive, and laminate |
| JP2016035046A (en) * | 2014-08-01 | 2016-03-17 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． | Adhesive composition, optical member and adhesive sheet |
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| JP2005264109A (en) | 2004-03-22 | 2005-09-29 | Hitachi Chem Co Ltd | Film-shaped adhesive and manufacturing method of semiconductor device using the same |
| CN104428331B (en) * | 2012-07-11 | 2019-02-15 | 东洋油墨Sc控股株式会社 | Active energy beam polymer resin composition and the laminated body for using the resin combination |
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| JP2001003031A (en) * | 1999-06-22 | 2001-01-09 | Bridgestone Corp | Pressure-sensitive adhesive composition, film coated with pressure-sensitive adhesive, and method for sticking film coated with pressure-sensitive adhesive |
| JP2001019821A (en) * | 1999-07-05 | 2001-01-23 | Sumitomo Bakelite Co Ltd | Die attach paste and semiconductor device using the same |
| JP2012097162A (en) * | 2010-10-29 | 2012-05-24 | Cheil Industries Inc | Adhesive composition |
| JP2012140589A (en) * | 2010-12-29 | 2012-07-26 | Cheil Industries Inc | Anisotropic conductive film, anisotropic conductive film composition included in the same, and device using the same |
| KR20120077053A (en) * | 2010-12-30 | 2012-07-10 | 제일모직주식회사 | Adhesive composition and optical member using the same |
| WO2014010524A1 (en) * | 2012-07-11 | 2014-01-16 | タツタ電線株式会社 | Curable electroconductive adhesive composition, electromagnetic shielding film, electroconductive adhesive film, adhesion method, and circuit board |
| JP2014201701A (en) * | 2013-04-08 | 2014-10-27 | 東洋インキＳｃホールディングス株式会社 | Resin composition, active energy ray-polymerizable adhesive, and laminate |
| JP2016035046A (en) * | 2014-08-01 | 2016-03-17 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． | Adhesive composition, optical member and adhesive sheet |
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| Publication number | Publication date |
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| KR20200120729A (en) | 2020-10-21 |
| WO2019193880A1 (en) | 2019-10-10 |
| KR102522875B1 (en) | 2023-04-18 |
| TW201943825A (en) | 2019-11-16 |
| CN111868198B (en) | 2023-06-23 |
| JP7264598B2 (en) | 2023-04-25 |
| CN111868198A (en) | 2020-10-30 |
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