JP2008201884A - Flame-retardant adhesive composition, flexible copper-clad laminated plate, cover-lay, and adhesive sheet - Google Patents
Flame-retardant adhesive composition, flexible copper-clad laminated plate, cover-lay, and adhesive sheet Download PDFInfo
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- JP2008201884A JP2008201884A JP2007039176A JP2007039176A JP2008201884A JP 2008201884 A JP2008201884 A JP 2008201884A JP 2007039176 A JP2007039176 A JP 2007039176A JP 2007039176 A JP2007039176 A JP 2007039176A JP 2008201884 A JP2008201884 A JP 2008201884A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 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 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- -1 amine imide Chemical class 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000004760 aramid Substances 0.000 claims description 9
- 229920003235 aromatic polyamide Polymers 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims 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 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Chemical class 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000004840 adhesive resin Substances 0.000 claims 2
- 229920006223 adhesive resin Polymers 0.000 claims 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 abstract description 5
- 238000009413 insulation Methods 0.000 abstract description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 2
- 239000012787 coverlay film Substances 0.000 description 14
- 239000010408 film Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052787 antimony Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical class [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は、ハロゲンフリーの難燃性接着剤組成物ならびにそれを用いたフレキシブル銅張積層板、カバーレイ、および接着剤シートに関する。 The present invention relates to a halogen-free flame-retardant adhesive composition and a flexible copper-clad laminate, coverlay, and adhesive sheet using the same.
フレキシブルプリント配線板は、フレキシブル銅張積層板、カバーレイおよび接着剤シートにより構成される。このような用途で用いられる接着剤にはエポキシ樹脂を主成分とした物が一般に使用されており、難燃性の規格を達成するために、難燃剤やその補助剤が添加される。難燃剤としては臭素系のハロゲン化合物が一般的であり、ハロゲン化合物と水酸化アルミニウムなどの金属水和物とを併用したものも用いられる。また、難燃剤の補助剤として、アンチモン化合物が用いられる。
しかし、上述した難燃剤や補助剤は、燃焼時に有害な臭素化水素やブロム化ダイオキシン、フラン類、アンチモンガスを発生する可能性がある。近年、環境問題、人体に対する安全性について関心が高まり、従来の難燃性を維持したまま、より少ない有害性、より高い信頼性、すなわちハロゲンフリーの難燃性接着剤組成物が求められている。 However, the above-mentioned flame retardants and adjuvants may generate harmful hydrogen bromide, brominated dioxins, furans, and antimony gas during combustion. In recent years, there has been a growing interest in environmental issues and safety to the human body, and there is a need for flame retardant adhesive compositions that are less harmful and more reliable, that is, halogen-free, while maintaining conventional flame retardancy. .
また、接着剤組成物には、接着性、可とう性を付与するために、アクリロニトリルブタジエンゴムやアクリルゴムなどの架橋ゴムが用いられている。しかしながら、上記従来技術では、高密度化のため配線層が微細化されると、配線層の金属成分が絶縁層中を移動するマイグレーションを起こし、配線間での絶縁抵抗値が低下しやすくなるという問題があった。 In addition, in the adhesive composition, a crosslinked rubber such as acrylonitrile butadiene rubber or acrylic rubber is used in order to impart adhesiveness and flexibility. However, in the above prior art, when the wiring layer is miniaturized for higher density, the metal component of the wiring layer undergoes migration that moves in the insulating layer, and the insulation resistance value between the wirings is likely to decrease. There was a problem.
本発明は、このような事情に鑑みてなされたものであって、ハロゲン化合物を含有することなく優れた難燃性と高い電気絶縁信頼性を有し、しかもフレキシブルプリント配線板に必要とされる特性に関しても優れるハロゲンフリー接着剤組成物、ならびにそれを用いたフレキシブル銅張積層板、カバーレイおよび接着剤シートを提供することを目的とする。 The present invention has been made in view of such circumstances, and has excellent flame retardancy and high electrical insulation reliability without containing a halogen compound, and is required for a flexible printed wiring board. It is an object of the present invention to provide a halogen-free adhesive composition that is also excellent in properties, and a flexible copper-clad laminate, coverlay, and adhesive sheet using the same.
本発明の難燃性接着剤組成物は、（Ａ）非ハロゲン系エポキシ樹脂、（Ｂ）ポリウレタン樹脂、（Ｃ）硬化剤、（Ｄ）硬化促進剤、（Ｅ）リン系難燃剤および（Ｆ）無機充填剤を含有するハロゲンフリーの難燃性接着剤組成物において、（Ｂ）ポリウレタン樹脂は水酸基価が５．０〜１５．０ＫＯＨｍｇ／ｇを有する樹脂であり、リン元素の全有機樹脂成分に対する割合が０．５〜４．０重量％であることを特徴とする。 The flame retardant adhesive composition of the present invention comprises (A) a non-halogen epoxy resin, (B) a polyurethane resin, (C) a curing agent, (D) a curing accelerator, (E) a phosphorus flame retardant, and (F ) In the halogen-free flame retardant adhesive composition containing an inorganic filler, (B) polyurethane resin is a resin having a hydroxyl value of 5.0 to 15.0 KOHmg / g, and is an all-organic resin component of phosphorus element The ratio is 0.5 to 4.0% by weight.
（Ａ）成分の非ハロゲン系エポキシ樹脂としては、グリシジルエーテル系エポキシ樹脂が好適である。そのようなエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などが含まれる。また、グリシジルエーテル系の変性エポキシ樹脂も含まれる。これらは１種だけでもよく、２種以上を併用することもできる。また、リン含有エポキシ樹脂も有効に用いることができる。ただし、本発明はこれらのエポキシ樹脂に限定されるものではない。 As the non-halogen epoxy resin as the component (A), a glycidyl ether epoxy resin is suitable. Such epoxy resins include bisphenol A type epoxy resins, bisphenol F type resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like. Also included are glycidyl ether-based modified epoxy resins. These may be used alone or in combination of two or more. Also, phosphorus-containing epoxy resins can be used effectively. However, the present invention is not limited to these epoxy resins.
（Ｂ）成分のポリウレタン樹脂としては、水酸基価が上述の範囲のものであれば特にその種類は限定されず、熱可塑性でも官能基を持った熱硬化性のものでもよく、リンを含有したものでも良い。これらは１種だけでもよく、２種以上を併用することもできる。 The polyurethane resin of component (B) is not particularly limited as long as the hydroxyl value is in the above range, and may be thermoplastic or thermosetting with a functional group, and contains phosphorus. But it ’s okay. These may be used alone or in combination of two or more.
（Ｃ）成分の硬化剤としては、エポキシ樹脂の硬化剤として通常使用されるものであれば特に限定はされず、例えば、ジシアンジアミドとその誘導体、ノボラック型フェノール樹脂、アミノ変性ノボラック型フェノール樹脂、ポリビニルフェノール樹脂、有機酸ヒドラシッド、ジアミノマレオニトリルとその誘導体、メラミンとその誘導体、アミンイミド、ポリアミン塩、モレキュラーシーブ、アミン、酸無水物、ポリアミド、イミダゾールなどの１種類または２種類以上を用いることができる。 The curing agent for component (C) is not particularly limited as long as it is usually used as a curing agent for epoxy resins. For example, dicyandiamide and its derivatives, novolac-type phenol resins, amino-modified novolac-type phenol resins, polyvinyl One type or two or more types such as phenol resin, organic acid hydracid, diaminomaleonitrile and derivatives thereof, melamine and derivatives thereof, amine imide, polyamine salt, molecular sieve, amine, acid anhydride, polyamide, and imidazole can be used.
（Ｄ）成分の硬化促進剤としては、（Ａ）非ハロゲン系エポキシ樹脂と（Ｃ）硬化剤との反応の促進剤に用いられる物であれば特に限定されず、例えば、第三アミン、イミダゾール、芳香族アミンのうち１種または２種以上用いることができる。 The (D) component curing accelerator is not particularly limited as long as it is used as an accelerator for the reaction between the (A) non-halogen epoxy resin and the (C) curing agent, and examples thereof include tertiary amines and imidazoles. One or two or more of aromatic amines can be used.
（Ｅ）成分のリン系難燃剤としては、特に限定されるものではないが、リン酸エステル化合物、ホスファゼン化合物、ホスファネート、ホスフィン酸化合物が好ましい。また、ホスホン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物などの有機リン化合物なども好適に用いることができ、これらを１種または２種以上を使用することができる。 Although it does not specifically limit as a phosphorus flame retardant of (E) component, A phosphate ester compound, a phosphazene compound, a phosphanate, and a phosphinic acid compound are preferable. Moreover, organophosphorus compounds, such as a phosphonic acid compound, a phosphine oxide compound, and a phospholane compound, can also be used suitably and these can use 1 type (s) or 2 or more types.
（Ｆ）成分の無機充填剤としては、難燃性などの補助添加剤として使用する無機充填剤であり、従来からフレキシブル銅張積層板またはカバーレイフィルムに使用されているものであれば特に限定されるものではなく、難燃性の観点から、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、酸化マグネシウム、タルク、クレー、シリカ、ハイドロタルサイトなどが好ましい。これらは１種または２種以上で使用することができる。 The inorganic filler of component (F) is an inorganic filler used as an auxiliary additive such as flame retardancy, and is particularly limited as long as it is conventionally used for flexible copper-clad laminates or coverlay films. However, from the viewpoint of flame retardancy, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, talc, clay, silica, hydrotalcite and the like are preferable. These can be used alone or in combination of two or more.
本発明の接着剤組成物には、必要に応じて、顔料、酸化防止剤などを添加することができる。 If necessary, pigments, antioxidants, and the like can be added to the adhesive composition of the present invention.
本発明では、必要に応じて、表面処理剤を用いることもできる。表面処理剤の使用方法としては、特に限定されるものではないが、充填剤にあらかじめ表面処理を施したり、ワニスに添加するなどの方法がある。表面活性剤としては、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−アミノプロピルトリメトキシシランなどを１種または２種以上で使用することができる。 In the present invention, a surface treatment agent may be used as necessary. The method of using the surface treatment agent is not particularly limited, and there are methods such as pre-treatment of the filler or addition to the varnish. As the surfactant, one or more of γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc. should be used. Can do.
接着剤の溶剤として、トルエン、キシレン、メチルエチルケトン、エチレングリコールモノメチルエーテル、Ｎ，Ｎ−ジメチルホルムアルデヒドおよびその混合物等を使用することができる。 As a solvent for the adhesive, toluene, xylene, methyl ethyl ketone, ethylene glycol monomethyl ether, N, N-dimethylformaldehyde and a mixture thereof can be used.
本発明の難燃性接着剤組成物は、ポリイミドフィルムおよび／またはアラミドフィルムの少なくとも片面に接着剤により銅箔が接着されたフレキシブル銅張積層板における接着剤、ポリイミドフィルムおよび／またはアラミドフィルムに接着剤が塗布されたカバーレイフィルムにおける接着剤、あるいは、非ハロゲン樹脂の離型フィルムに接着剤が塗布された接着剤シートにおける接着剤として利用することができる。 The flame-retardant adhesive composition of the present invention is bonded to an adhesive, a polyimide film and / or an aramid film in a flexible copper-clad laminate in which a copper foil is bonded to at least one surface of a polyimide film and / or an aramid film with an adhesive. It can be used as an adhesive in a cover lay film coated with an adhesive, or an adhesive in an adhesive sheet coated with an adhesive on a non-halogen resin release film.
本発明の難燃性接着剤組成物は、ポリイミドフィルムおよび／またはアラミドフィルムの少なくとも片面に接着剤により銅箔が貼り合わされたフレキシブル銅張積層板における接着剤、ポリイミドフィルムおよび／またはアラミドフィルムの表面に樹脂層を形成したカバーレイにおける樹脂層、シート状に形成された接着剤シート、ポリイミドフィルムおよび／またはアラミドフィルムの少なくとも片面に接着剤により銅箔が貼り合わされた回路が形成されたフレキシブルプリント配線板における接着剤として利用することができる。フレキシブルプリント配線板上には、上述のカバーレイを貼り合わせることができる。フレキシブルプリント配線板と補強板とを上述の接着剤シートを介して貼り合わせることができる。 The flame-retardant adhesive composition of the present invention is a surface of an adhesive, a polyimide film and / or an aramid film in a flexible copper-clad laminate in which a copper foil is bonded to at least one surface of a polyimide film and / or an aramid film with an adhesive. Flexible printed wiring in which a circuit in which a copper foil is bonded to at least one surface of a resin layer, a sheet-like adhesive sheet, a polyimide film and / or an aramid film in a cover lay having a resin layer formed thereon is formed It can be used as an adhesive on a plate. The above-mentioned coverlay can be bonded on the flexible printed wiring board. A flexible printed wiring board and a reinforcement board can be bonded together through the above-mentioned adhesive sheet.
ポリイミドフィルムおよび／またはアラミドフィルムの片面もしくは両面に、プラズマ処理、コロナ放電処理、サンドブラスト処理、ウェットブラスト処理等の表面加工を施しても良い。 One or both surfaces of the polyimide film and / or the aramid film may be subjected to surface processing such as plasma treatment, corona discharge treatment, sand blast treatment, wet blast treatment or the like.
本発明によれば、ハロゲン化合物を含有することなく優れた難燃性と高い電気絶縁信頼性を有し、しかもフレキシブルプリント配線板に必要とされる特性に関しても優れたハロゲンフリーの難燃性接着剤組成物、ならびにそれを用いたフレキシブル銅張積層板、カバーレイおよび接着剤シートを提供することができる。本発明はエレクトロニクス製品の高性能化に特に効果がある。 According to the present invention, halogen-free flame-retardant adhesion has excellent flame retardancy and high electrical insulation reliability without containing a halogen compound, and also has excellent properties required for flexible printed wiring boards. An agent composition, and a flexible copper-clad laminate, a coverlay and an adhesive sheet using the same can be provided. The present invention is particularly effective in improving the performance of electronic products.
次に、本発明のフレキシブルプリント配線板材料の製造方法について説明する。図１ないし図３はそれぞれフレキシブル銅張積層板、カバーレイフィルムおよび接着剤シートの断面図を示す。 Next, the manufacturing method of the flexible printed wiring board material of this invention is demonstrated. 1 to 3 show sectional views of a flexible copper-clad laminate, a coverlay film, and an adhesive sheet, respectively.
フレキシブルプリント銅張積層板を製造するには、（Ａ）非ハロゲン系エポキシ樹脂、（Ｂ）ポリウレタン樹脂、（Ｃ）硬化剤、（Ｄ）硬化促進剤、（Ｅ）リン系難燃剤および（Ｆ）無機充填剤を含有し、（Ｂ）ポリウレタン樹脂は水酸基価が５．０〜１５．０ＫＯＨｍｇ／ｇを有する樹脂であり、リン元素の全有機樹脂成分に対する割合が０．５〜４．０重量％である難燃性接着剤組成物をあらかじめ調製しておき、これに所定量の溶剤を添加して得られた接着剤溶液をフィルム１１上に塗布して接着剤層１２とし、熱ロールで銅箔１３を片面または両面に張り合わせた後に、加熱硬化する。カバーレイを製造するには、上記の接着剤溶液をフィルム２１に塗布して接着剤層２２とし、加熱乾燥する。接着剤シートは、接着剤溶液をキャリアフィルム３１上に塗布して接着剤層３２とし、加熱乾燥して剥離することにより製造される。
To produce a flexible printed copper clad laminate, (A) a non-halogen epoxy resin, (B) a polyurethane resin, (C) a curing agent, (D) a curing accelerator, (E) a phosphorus flame retardant, and (F ) Containing inorganic filler, (B) polyurethane resin is a resin having a hydroxyl value of 5.0-15.0 KOHmg / g, and the ratio of phosphorus element to the total organic resin component is 0.5-4.0 wt. % Flame retardant adhesive composition is prepared in advance, and an adhesive solution obtained by adding a predetermined amount of solvent thereto is applied on the
本発明の具体的な実施例および比較例について以下に詳しく説明する。なお、以下の実施例は単なる例示であり、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例および比較例において、「部」とは「重量部」を意味する。 Specific examples and comparative examples of the present invention will be described in detail below. The following examples are merely illustrative, and the present invention is not limited to these examples. In the following examples and comparative examples, “part” means “part by weight”.
［実施例１］
エポキシ当量５０３、リン含有率３％のリン含有エポキシ樹脂（ＦＸ−３０５：東都化成社製、商品名）１００部、エポキシ当量４７５のビスフェノールＡ型エポキシ樹脂（エピクロン１０５１：大日本インキ化学工業社製、商品名）５０部、エポキシ当量１８８のビフェニルノボラック型エポキシ樹脂（ＮＣ３０００Ｈ：日本化薬社製、商品名）５０部、水酸基価１０ＫＯＨｍｇ／ｇのポリウレタン樹脂（ＵＲ３５００：東洋紡績社製、商品名）２３０部、水酸基価２８９の４，４’−ジアミノジフェニルスルホン（和歌山精化工業社製）２００部、２−エチル−４メチルイミダゾール０．１部、リン含有率１３％のホスファゼン化合物（ＳＰＢ−１００：大塚化学社製、商品名）１５０部をメチルエチルケトン６４０部に溶解攪拌し、樹脂溶解物とする。この樹脂溶解物にさらに水酸化アルミニウム（ハイジライトＨ−４２Ｍ：昭和電工社製、商品名）３４０部を添加攪拌し、接着剤とする。この接着剤のリン含有率は３．７重量％である。
[Example 1]
100 parts of a phosphorus-containing epoxy resin having an epoxy equivalent of 503 and a phosphorus content of 3% (FX-305: manufactured by Tohto Kasei Co., Ltd., trade name) and a bisphenol A type epoxy resin having an epoxy equivalent of 475 (Epicron 1051: manufactured by Dainippon Ink & Chemicals, Inc.) , Trade name) 50 parts, epoxy equivalent 188 biphenyl novolac type epoxy resin (NC3000H: Nippon Kayaku Co., Ltd., trade name) 50 parts, hydroxyl value 10 KOHmg / g polyurethane resin (UR3500: manufactured by Toyobo Co., Ltd., trade name) 230 parts, 200 parts of 4,4′-diaminodiphenylsulfone having a hydroxyl value of 289 (manufactured by Wakayama Seika Kogyo Co., Ltd.), 0.1 part of 2-ethyl-4methylimidazole, a phosphazene compound having a phosphorus content of 13% (SPB-100) : Otsuka Chemical Co., Ltd., trade name) 150 parts of methyl ethyl ketone dissolved in 640 parts and stirred, resin Let it be a lysate. Further, 340 parts of aluminum hydroxide (Hijilite H-42M: trade name, manufactured by Showa Denko KK) is added to the resin melt and stirred to obtain an adhesive. The phosphorus content of this adhesive is 3.7% by weight.
この接着剤を乾燥後１５μｍの塗工厚さになるように、厚さ２５μｍのポリイミドフィルム（カプトンＫ−１００Ｖ：デュポン社製、商品名）に塗工し、１２０℃、１０分乾燥した。その後、厚さ３５μｍの電解銅箔を積層し、１６０℃、１０分、圧力４ＭＰａでプレス成形し、１５０℃、１６時間加熱してアフターキュアさせることにより、フレキシブル銅張積層板を得た。 This adhesive was coated on a 25 μm thick polyimide film (Kapton K-100V: trade name, manufactured by DuPont) so as to have a coating thickness of 15 μm after drying, and dried at 120 ° C. for 10 minutes. Thereafter, an electrolytic copper foil having a thickness of 35 μm was laminated, press-molded at 160 ° C. for 10 minutes and at a pressure of 4 MPa, and heated and cured at 150 ° C. for 16 hours to obtain a flexible copper-clad laminate.
また、同じ接着剤を使用し、乾燥後２５μｍの塗工厚さになるように、厚さ２５μｍのポリイミドフィルム（カプトンＫ−１００Ｖ：デュポン社製、商品名）に塗工し、１２０℃、１０分乾燥することで、各接着剤を使用したカバーレイフィルムを得た。 In addition, using the same adhesive, it was applied to a polyimide film (Kapton K-100V: DuPont, trade name) having a thickness of 25 μm so as to have a coating thickness of 25 μm after drying. By partially drying, a coverlay film using each adhesive was obtained.
［実施例２］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりに水酸基価６ＫＯＨｍｍｇ／ｇのポリウレタン樹脂（ＵＲ８２００：東洋紡績社製、商品名）２３０部を使用し、それ以外は実施例１と同様に、フレキシブル銅張積層板およびカバーレイフィルムを得た。
[Example 2]
Instead of the polyurethane resin (UR3500) of Example 1, 230 parts of a polyurethane resin having a hydroxyl value of 6 KOHmmg / g (UR8200: product name, manufactured by Toyobo Co., Ltd.) was used. A laminate and a coverlay film were obtained.
［実施例３］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりに水酸基価６ＫＯＨｍｍｇ／ｇのポリウレタン樹脂（ＵＲ８２００：東洋紡績社製、商品名）２３０部を、ビフェニルノボラック型エポキシ樹脂（ＮＣ３０００Ｈ）の替わりにエポキシ当量１８０のフェノールノボラック型エポキシ樹脂（エピクロンＮ−７４０：大日本インキ化学工業社製、商品名）５０部を使用し、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。
[Example 3]
Instead of the polyurethane resin of Example 1 (UR3500), 230 parts of a polyurethane resin (UR8200: manufactured by Toyobo Co., Ltd., trade name) having a hydroxyl value of 6 KOH mmg / g was used. A flexible copper-clad laminate and a coverlay film were obtained in the same manner as in Example 1 except that 50 parts of phenol novolac type epoxy resin (Epicron N-740: trade name, manufactured by Dainippon Ink and Chemicals, Inc.) was used.
［実施例４］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりに水酸基価６ＫＯＨｍｍｇ／ｇのポリウレタン樹脂（ＵＲ８２００：東洋紡績社製、商品名）２３０部を、水酸基価２８９の４，４’−ジアミノジフェニルスルホンの替わりに水酸基価１４６のフェノライト（ＬＡ−１３５６：大日本インキ化学工業社製、商品名）２００部を使用し、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。
[Example 4]
Instead of the polyurethane resin of Example 1 (UR3500), 230 parts of a polyurethane resin having a hydroxyl value of 6 KOHmmg / g (UR8200: product name, manufactured by Toyobo Co., Ltd.) is used instead of 4,4′-diaminodiphenylsulfone having a hydroxyl value of 289. A flexible copper clad laminate and a coverlay film were obtained in the same manner as in Example 1 except that 200 parts of phenolite having a hydroxyl value of 146 (LA-1356: trade name, manufactured by Dainippon Ink and Chemicals, Inc.) was used.
［比較例１］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりに水酸基価２ＫＯＨｍｍｇ／ｇのポリウレタン樹脂（ＵＲ１４００：東洋紡績社製、商品名）を使用し、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。
[Comparative Example 1]
Instead of the polyurethane resin (UR3500) of Example 1, a polyurethane resin having a hydroxyl value of 2 KOHmmg / g (UR1400: product name, manufactured by Toyobo Co., Ltd.) was used, and other than that, a flexible copper-clad laminate and A coverlay film was obtained.
［比較例２］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりに水酸基価１７ＫＯＨｍｍｇ／ｇのポリウレタン樹脂（ＵＲ５５３７：東洋紡績社製、商品名）を使用し、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。
[Comparative Example 2]
Instead of the polyurethane resin of Example 1 (UR3500), a polyurethane resin having a hydroxyl value of 17 KOHmmg / g (UR5537: product name, manufactured by Toyobo Co., Ltd.) was used. Otherwise, a flexible copper-clad laminate and A coverlay film was obtained.
［比較例３］
実施例１のポリウレタン樹脂（ＵＲ３５００）の替わりにカルボキシル基含有アクリルニトリルブタジエンゴム（ニポール１０７２Ｊ：日本ゼオン社製、商品名）２３０部を使用し、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。
[Comparative Example 3]
In place of the polyurethane resin (UR3500) of Example 1, 230 parts of carboxyl group-containing acrylonitrile butadiene rubber (Nipol 1072J: trade name, manufactured by Nippon Zeon Co., Ltd.) was used. Otherwise, flexible copper-clad laminate as in Example 1 A plate and coverlay film were obtained.
［比較例４］
実施例１のリン含有エポキシ樹脂（ＦＸ−３０５）を１００部から０部に、ビスフェノールＡ型エポキシ樹脂（エピクロン１０５１）５０部を１５０部に、ホスファゼン化合物（ＳＰＢ−１００）１６０部を１０部にし、それ以外は実施例１と同様にフレキシブル銅張積層板およびカバーレイフィルムを得た。接着剤中のリン含有率は0．３重量％である。
[Comparative Example 4]
From 100 parts to 0 part of the phosphorus-containing epoxy resin (FX-305) of Example 1, 50 parts of bisphenol A type epoxy resin (Epiclon 1051) to 150 parts, and 160 parts of phosphazene compound (SPB-100) to 10 parts. Otherwise, a flexible copper clad laminate and a coverlay film were obtained in the same manner as in Example 1. The phosphorus content in the adhesive is 0.3% by weight.
［比較例５］
実施例１のホスファゼン化合物（ＳＰＢ−１００）１６０部を２５０部にし、それ以外は実施例１と同様にフレキシブル積層板およびカバーレイフィルムを得た。接着剤のリン含有率は５．０重量％である。
[Comparative Example 5]
A flexible laminate and a coverlay film were obtained in the same manner as in Example 1 except that 160 parts of the phosphazene compound (SPB-100) of Example 1 was changed to 250 parts. The phosphorus content of the adhesive is 5.0% by weight.
［試験例］
以上の実施例および比較例のそれぞれのフレキシブル銅張積層板に関して、引き剥がし強さ、はんだ耐熱性、耐燃性、およびマイグレーション性を評価した。試験の詳細は以下の通りである。
（１）引き剥がし強さ
各フレキシブル銅張積層板について、ＪＩＳ、Ｃ−６４８１に従い、銅パターン幅３ｍｍで９０度引き剥がし強さを評価した。
（２）はんだ耐熱性
各フレキシブル銅張積層板を１０５℃、１時間乾燥した後、２６０℃のはんだ浴に３０秒浮かべて膨れを確認した。
（３）耐燃性
各フレキシブル銅張積層板について、ＵＬ規格９４準拠の方法に従い、耐燃性を評価した。
（４）耐マイグレーション性
１．試験装置として、５０Ｖを±１％の範囲で供給できる直流電源と、８５±２℃、８５±３％に調整できる恒温恒湿槽とを用い、
２．各実施例、比較例におけるフレキシブル銅張積層板に試験用に回路間隔が７５μｍの櫛形電極を作製し、同じ接着剤で作製したカバーレイフィルムを積層し、１６０℃、６０分、４ＭＰａでプレス接着したものをサンプルとし、
３．これらのサンプルを恒温恒湿槽に投入し、電極間に５０Ｖの直流電圧を１０００時間印加し、印加前と印加後の電極間を顕微鏡観察した。デンドライドの発生があるものは×とし、無い物は〇と評価した。印加後の絶縁抵抗値も恒温恒湿槽内で連続測定し、１０2ＭΩ未満は×とし１０2ＭΩ以上を〇と評価した。
[Test example]
For each of the flexible copper-clad laminates of the above examples and comparative examples, the peel strength, solder heat resistance, flame resistance, and migration were evaluated. The details of the test are as follows.
(1) Peeling strength About each flexible copper clad laminated board, 90 degree peeling strength was evaluated by copper pattern width 3mm according to JIS and C-6481.
(2) Solder heat resistance Each flexible copper clad laminate was dried at 105 ° C. for 1 hour and then floated in a solder bath at 260 ° C. for 30 seconds to confirm swelling.
(3) Flame resistance About each flexible copper clad laminated board, the flame resistance was evaluated according to the method of UL standard 94 conformity.
(4) Migration resistance Using a DC power supply that can supply 50V in a range of ± 1% and a constant temperature and humidity chamber that can be adjusted to 85 ± 2 ° C. and 85 ± 3%,
2. Comb electrodes with a circuit interval of 75 μm were prepared for testing on flexible copper-clad laminates in each example and comparative example, and a coverlay film produced with the same adhesive was laminated, and press bonded at 160 ° C. for 60 minutes at 4 MPa. Sampled
3. These samples were put into a constant temperature and humidity chamber, a 50 V DC voltage was applied between the electrodes for 1000 hours, and the electrodes before and after the application were observed with a microscope. The case where dendride was generated was evaluated as x, and the case where there was no dendride was evaluated as ◯. The insulation resistance value after application was also continuously measured in a constant temperature and humidity chamber. Less than 10 2 MΩ was evaluated as x, and 10 2 MΩ or more was evaluated as ◯.
以上の試験の結果を実施例に関して表１に、比較例に関して表２に示す。 The results of the above tests are shown in Table 1 for the examples and Table 2 for the comparative examples.
１１、２１ フィルム
１２、２２、３２ 接着剤層
１３ 銅箔
３１ キャリアフィルム
11, 21
Claims (12)
（Ｂ）ポリウレタン樹脂、
（Ｃ）硬化剤、
（Ｄ）硬化促進剤、
（Ｅ）リン系難燃剤および
（Ｆ）無機充填剤
を含有するハロゲンフリーの難燃性接着剤組成物において、
（Ｂ）ポリウレタン樹脂は水酸基価が５．０〜１５．０ＫＯＨｍｇ／ｇを有する樹脂であり、
リン元素の全有機樹脂成分に対する割合が０．５〜４．０重量％である
ことを特徴とする難燃性接着剤組成物。 (A) non-halogen epoxy resin,
(B) polyurethane resin,
(C) a curing agent,
(D) a curing accelerator,
In the halogen-free flame-retardant adhesive composition containing (E) a phosphorus-based flame retardant and (F) an inorganic filler,
(B) The polyurethane resin is a resin having a hydroxyl value of 5.0 to 15.0 KOHmg / g,
The ratio with respect to the total organic resin component of a phosphorus element is 0.5 to 4.0 weight%. The flame-retardant adhesive composition characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007039176A JP2008201884A (en) | 2007-02-20 | 2007-02-20 | Flame-retardant adhesive composition, flexible copper-clad laminated plate, cover-lay, and adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007039176A JP2008201884A (en) | 2007-02-20 | 2007-02-20 | Flame-retardant adhesive composition, flexible copper-clad laminated plate, cover-lay, and adhesive sheet |
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| JP2008201884A true JP2008201884A (en) | 2008-09-04 |
Family
ID=39779715
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007039176A Pending JP2008201884A (en) | 2007-02-20 | 2007-02-20 | Flame-retardant adhesive composition, flexible copper-clad laminated plate, cover-lay, and adhesive sheet |
Country Status (1)
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| JP (1) | JP2008201884A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010143988A (en) * | 2008-12-17 | 2010-07-01 | Toagosei Co Ltd | Adhesive composition and cover-lay film and flexible copper-clad laminate using the same |
| JP2010150437A (en) * | 2008-12-26 | 2010-07-08 | Toagosei Co Ltd | Adhesive composition, and cover lay film and flexible copper-clad laminate, both prepared by using the composition |
| JP2015007226A (en) * | 2013-05-29 | 2015-01-15 | 荒川化学工業株式会社 | Removable urethane adhesive composition, and removable adhesive film and surface protective film of optical component obtained by using the composition |
| KR101848571B1 (en) | 2016-12-28 | 2018-05-29 | 한국신발피혁연구원 | A TPU Resin Composite Using Halogen Free Type Flame Retardant |
| CN109280529A (en) * | 2018-09-28 | 2019-01-29 | 五邑大学 | A kind of glue and preparation method thereof of copper-clad plate aluminum substrate |
| KR20190076532A (en) * | 2017-12-22 | 2019-07-02 | 한국신발피혁연구원 | A thermoplastic polyurethane resin composite with flame retardancy and a method of producing the same |
| US10947428B2 (en) | 2010-11-19 | 2021-03-16 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
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| JP2001019930A (en) * | 1999-07-12 | 2001-01-23 | Toshiba Chem Corp | Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive film |
| JP2002129126A (en) * | 2000-10-23 | 2002-05-09 | Tomoegawa Paper Co Ltd | Adhesive composition and adhesive sheet for semiconductor device |
| JP2005015595A (en) * | 2003-06-25 | 2005-01-20 | Nitsukan Kogyo Kk | Material for halogen-free flexible printed wiring board |
| JP2005125724A (en) * | 2003-10-20 | 2005-05-19 | Toyobo Co Ltd | Laminate |
| JP2007051212A (en) * | 2005-08-17 | 2007-03-01 | Shin Etsu Chem Co Ltd | Adhesive composition and coverlay film and adhesive sheet using the same |
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2007
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001019930A (en) * | 1999-07-12 | 2001-01-23 | Toshiba Chem Corp | Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive film |
| JP2002129126A (en) * | 2000-10-23 | 2002-05-09 | Tomoegawa Paper Co Ltd | Adhesive composition and adhesive sheet for semiconductor device |
| JP2005015595A (en) * | 2003-06-25 | 2005-01-20 | Nitsukan Kogyo Kk | Material for halogen-free flexible printed wiring board |
| JP2005125724A (en) * | 2003-10-20 | 2005-05-19 | Toyobo Co Ltd | Laminate |
| JP2007051212A (en) * | 2005-08-17 | 2007-03-01 | Shin Etsu Chem Co Ltd | Adhesive composition and coverlay film and adhesive sheet using the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010143988A (en) * | 2008-12-17 | 2010-07-01 | Toagosei Co Ltd | Adhesive composition and cover-lay film and flexible copper-clad laminate using the same |
| JP2010150437A (en) * | 2008-12-26 | 2010-07-08 | Toagosei Co Ltd | Adhesive composition, and cover lay film and flexible copper-clad laminate, both prepared by using the composition |
| US10947428B2 (en) | 2010-11-19 | 2021-03-16 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
| US11629276B2 (en) | 2010-11-19 | 2023-04-18 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
| JP2015007226A (en) * | 2013-05-29 | 2015-01-15 | 荒川化学工業株式会社 | Removable urethane adhesive composition, and removable adhesive film and surface protective film of optical component obtained by using the composition |
| KR101848571B1 (en) | 2016-12-28 | 2018-05-29 | 한국신발피혁연구원 | A TPU Resin Composite Using Halogen Free Type Flame Retardant |
| KR20190076532A (en) * | 2017-12-22 | 2019-07-02 | 한국신발피혁연구원 | A thermoplastic polyurethane resin composite with flame retardancy and a method of producing the same |
| KR102007219B1 (en) | 2017-12-22 | 2019-08-05 | 한국신발피혁연구원 | A thermoplastic polyurethane resin composite with flame retardancy and a method of producing the same |
| CN109280529A (en) * | 2018-09-28 | 2019-01-29 | 五邑大学 | A kind of glue and preparation method thereof of copper-clad plate aluminum substrate |
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