KR20090071774A - Resin composition for adhesives and use thereof - Google Patents
Resin composition for adhesives and use thereof Download PDFInfo
- Publication number
- KR20090071774A KR20090071774A KR1020070139658A KR20070139658A KR20090071774A KR 20090071774 A KR20090071774 A KR 20090071774A KR 1020070139658 A KR1020070139658 A KR 1020070139658A KR 20070139658 A KR20070139658 A KR 20070139658A KR 20090071774 A KR20090071774 A KR 20090071774A
- Authority
- KR
- South Korea
- Prior art keywords
- resin
- epoxy resin
- bismaleimide
- type epoxy
- resin composition
- 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.)
- Ceased
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 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 claims abstract description 13
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 15
- 239000011888 foil Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000009719 polyimide resin Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 claims description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 claims description 2
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 claims description 2
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 claims description 2
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- DBDVATPRBSPHIC-UHFFFAOYSA-N C1(=CC(=CC=C1)C=1C(=O)NC(C1)=O)C=1C(=O)NC(C1)=O.C1(=CC(=CC=C1)C=1C(=O)NC(C1)=O)C=1C(=O)NC(C1)=O Chemical compound C1(=CC(=CC=C1)C=1C(=O)NC(C1)=O)C=1C(=O)NC(C1)=O.C1(=CC(=CC=C1)C=1C(=O)NC(C1)=O)C=1C(=O)NC(C1)=O DBDVATPRBSPHIC-UHFFFAOYSA-N 0.000 claims 1
- JLBSVDZUWJLOCF-GTWSWNCMSA-N DDM-838 Chemical compound C1CCCNC(=O)C1NC(=O)CC(C)OC(=O)C(CCCCNC(=O)\C=C/CCCCCCCCCCCCCCCCC)NC(=O)C(N=1)(C)COC=1C1=CC=CC=C1O JLBSVDZUWJLOCF-GTWSWNCMSA-N 0.000 claims 1
- 238000007259 addition reaction Methods 0.000 claims 1
- 239000004840 adhesive resin Substances 0.000 claims 1
- 229920006223 adhesive resin Polymers 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BXCWPGGDRRAHII-UHFFFAOYSA-N 3,4-diethyl-2-methylbenzamide Chemical compound CCC1=CC=C(C(N)=O)C(C)=C1CC BXCWPGGDRRAHII-UHFFFAOYSA-N 0.000 description 1
- 101100172879 Caenorhabditis elegans sec-5 gene Proteins 0.000 description 1
- 101100172886 Caenorhabditis elegans sec-6 gene Proteins 0.000 description 1
- 101100172892 Caenorhabditis elegans sec-8 gene Proteins 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 monolime Chemical compound 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09J179/085—Unsaturated polyimide precursors
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 비스말레이미드; 에폭시 수지; 및 아민 경화제를 포함하는 접착제용 수지 조성물에 관한 것이다. 또한, 본 발명은 상기 접착제용 수지 조성물을 포함하는 수지 시트 및 상기 수지 시트를 포함하는 인쇄 회로 기판에 관한 것이다. 본 발명의 수지 조성물을 CCL(copper clad laminate), RCC (resin coated copper) 및 인쇄 회로 기판 등에서 접착제로 사용하면, 도전층과 수지 간의 접착 강도 및 내열성을 향상시킬 수 있다.The present invention is bismaleimide; Epoxy resins; And an resin composition for adhesives containing an amine curing agent. Moreover, this invention relates to the resin sheet containing the said resin composition for adhesive agents, and the printed circuit board containing the said resin sheet. When the resin composition of the present invention is used as an adhesive in a copper clad laminate (CCL), a resin coated copper (RCC), a printed circuit board, or the like, adhesive strength and heat resistance between the conductive layer and the resin can be improved.
Description
본 발명은 비스말레이미드와 에폭시 수지를 포함하는 접착제용 수지 조성물, 상기 접착제용 수지 조성물을 포함하는 수지 시트, 및 상기 수지 시트를 사용한 인쇄 회로 기판에 관한 것이다.TECHNICAL FIELD This invention relates to the resin composition for adhesives containing bismaleimide and an epoxy resin, the resin sheet containing the said resin composition for adhesives, and the printed circuit board using the said resin sheet.
최근, 전자 기기의 고성능화, 고기능화, 소형화가 진행되고 있으며, 이에 따라 사용되는 전자 부품에 대한 소형화, 경량화가 요구되고 있다. 따라서, 반도체 소자 패키지 방법이나 이들을 실장하는 배선 재료 또는 배선 부품도 보다 고밀도, 고기능, 또한 고성능의 것이 요구되고 있다. 특히, 반도체 패키지, MCM(multi chip module) 등의 고밀도 실장 재료, 인쇄 회로 기판 재료, 또는 자동차 부품의 고정 재료로서 사용 할 수 있는 양호한 접착성을 나타내는 재료가 요구되고 있다.In recent years, high performance, high functionality, and miniaturization of electronic devices have been progressed, and accordingly, miniaturization and weight reduction of electronic components used are required. Therefore, the semiconductor element package method, the wiring material or wiring components which mount them are also required to have a higher density, higher function, and higher performance. In particular, there is a demand for a material that exhibits good adhesion, which can be used as a semiconductor package, a high-density mounting material such as a multi chip module (MCM), a printed circuit board material, or an automobile component fixing material.
종래, 반도체 패키지나 그 밖의 실장 재료에 있어서, 양호한 기계적 특성 및 내열 특성, 절연 특성을 나타내는 접착제로서 아크릴계, 페놀계, 에폭시계, 폴리이미드계 수지 등의 접착제가 알려져 있다. 페놀계 및 에폭시계 접착제는 접착성이 우수하나, 유연성이 떨어지며, 아크릴계 접착제는 유연성은 우수하나 내열성이 낮 다는 문제가 있었다.Conventionally, adhesives, such as an acryl-type, a phenol type, an epoxy type, and polyimide resin, are known as an adhesive agent which shows favorable mechanical characteristics, heat resistance, and insulation characteristics in a semiconductor package or other mounting material. Phenolic and epoxy adhesives have excellent adhesion, but have low flexibility, and acrylic adhesives have a problem of excellent flexibility but low heat resistance.
이들 접착제의 문제점을 해결하기 위해, 폴리이미드 수지의 사용이 검토되고 있다. 폴리이미드 수지는 여러가지 유기 중합체 중에서도 내열성이 우수하므로, 우주, 항공 분야에서부터 전자 통신 분야에 이르기까지 폭넓게 이용되고 있으며, 접착제로도 사용되고 있다. 그러나, 내열성이 높은 폴리이미드 수지계 접착제는 접착하기 위해 300℃ 전후의 고온과 고압력을 필요로 하며, 접착력도 그다지 높다고 할 수 없다. 또한, 이미드 수지계 접착제를 반도체 패키지나 그 밖의 실장 재료로 사용하는 경우, 요구되는 땜납 내열성이나 PCT(압력 장치 테스트) 내성에 있어서도, 땜납 실장 후에 팽창되거나, PCT 후에 접착 강도가 저하된다는 문제가 있었다.In order to solve the problem of these adhesive agents, use of polyimide resin is examined. Since polyimide resin is excellent in heat resistance among various organic polymers, it is used widely from aerospace and aviation to an electronic communication field, and is also used as an adhesive agent. However, the polyimide resin adhesive having high heat resistance requires high temperature and high pressure around 300 ° C. in order to adhere, and the adhesive force is not so high. In addition, when an imide resin-based adhesive is used as a semiconductor package or other mounting material, there is a problem that the solder strength and the resistance to PCT (pressure device test) resistance also swell after solder mounting or the adhesive strength decreases after PCT. .
한편, 표면에 회로를 형성한 인쇄 회로 기판이 전자 부품이나 반도체 소자 등을 실장하기 위해 널리 사용되고 있다. 인쇄 회로 기판은 전자부품을 탑재하여 전자부품을 서로 전기적으로 접속시키는 역할을 하는 기판으로서, 전기 제품의 내부 부품으로서 매우 중요하다. On the other hand, a printed circuit board having a circuit formed on its surface is widely used for mounting electronic components, semiconductor elements, and the like. A printed circuit board is a board that mounts electronic components and serves to electrically connect the electronic components to each other, and is very important as an internal component of an electrical product.
일반적으로 인쇄 회로 기판은 배선 기판이나 회로를 보호하기 위한 보호막, 및 다층 구조의 배선 기판에 있어서의 각 층간의 절연성을 확보하기 위한 층간 절연막 등의 절연층이 형성된다. 또한, 상기 보호막이나 층간 절연막 등의 절연층은 접착성, 수지 유동성을 갖는 접착 재료를 이용하여 형성되는데, 기판 표면의 요철(조도)이 클수록 보호막이나 절연층과의 접착성이 양호해진다. 그런데, 최근 전자기기의 고성능화, 소형화, 다기능화 추세에 부합하기 위해서는 인쇄 회로 기판도 경박 단소화가 요구되며, 이에 따라 저조도 동박 또는 극박이 사용되고 있다. 이러 한 저조도 동박 또는 극박은 조도가 낮아 미세 패턴 형성에 용이하나, 접착 재료와의 접착 강도 및 내열성이 저하되어 공정 진행 중 회로의 박리 및 신뢰성에 문제가 된다. 따라서 이러한 문제점을 개선할 수 있는 접착 재료의 개발이 요구된다.Generally, a printed circuit board is provided with insulating layers, such as a protective film for protecting a wiring board and a circuit, and an interlayer insulation film for ensuring insulation between each layer in the wiring board of a multilayer structure. Insulating layers, such as the said protective film and an interlayer insulation film, are formed using the adhesive material which has adhesiveness and resin fluidity, but the larger the unevenness | corrugation (roughness) of a board | substrate surface, the better adhesiveness with a protective film or an insulating layer is. However, in order to meet the trend of high performance, miniaturization, and multifunction of electronic devices in recent years, light and short reduction of printed circuit boards is required. Accordingly, low light copper foil or ultrathin foil is used. Such low roughness copper foil or ultrathin is easy to form a fine pattern with low roughness, but the adhesive strength and heat resistance with the adhesive material are lowered, which is a problem in peeling and reliability of the circuit during the process. Therefore, the development of an adhesive material that can improve this problem is required.
상기 문제점을 해결하고자, 본 발명은 접착 강도 및 내열성이 우수한 접착제용 수지 조성물을 제공하고자 한다. 또한, 본 발명은 상기 수지 조성물을 포함하는 수지 시트, 및 상기 수지 시트를 사용한 인쇄 회로 기판을 제공하고자 한다.In order to solve the above problems, the present invention is to provide a resin composition for an adhesive excellent in adhesive strength and heat resistance. Moreover, this invention intends to provide the resin sheet containing the said resin composition, and the printed circuit board using the said resin sheet.
본 발명은 비스말레이미드(bismaleimide) 수지; 에폭시 수지; 및 아민 경화제를 포함하는 접착제용 수지 조성물을 제공한다. The present invention is bismaleimide resin; Epoxy resins; And it provides the resin composition for adhesives containing an amine hardener.
또한, 본 발명은 상기 접착제용 수지 조성물을 포함하는 수지 시트 및 상기 수지 시트를 포함하는 인쇄 회로 기판을 제공한다.Moreover, this invention provides the resin sheet containing the said resin composition for adhesives, and the printed circuit board containing the said resin sheet.
본 발명에 따른 수지 조성물은 접착제 용도로 사용할 수 있다. 특히, 본 발명의 수지 조성물을 CCL(copper clad laminate), RCC (resin coated copper) 및 인쇄 회로 기판 등에서 접착제로 사용하면, 도전층과 수지 간의 접착 강도 및 내열성을 향상시킬 수 있다.The resin composition according to the present invention can be used for adhesives. In particular, when the resin composition of the present invention is used as an adhesive in a copper clad laminate (CCL), a resin coated copper (RCC), a printed circuit board, or the like, the adhesive strength and heat resistance between the conductive layer and the resin can be improved.
본 발명의 수지 조성물은 비스말레이미드(bismaleimide) 수지; 에폭시 수지; 및 아민 경화제를 포함하는 접착제용 수지 조성물인 것이 특징이다. 또한, 본 발명의 접착제용 수지 조성물을 사용하면, 비스말레이미드에 의하여 주로 내열성이 확보 가능하고, 에폭시 및 아민 경화제에 의하여 접착 강도를 유지할 수 있다.The resin composition of the present invention is a bismaleimide resin; Epoxy resins; And a resin composition for an adhesive comprising an amine curing agent. Moreover, when using the resin composition for adhesive agents of this invention, heat resistance can be mainly ensured by bismaleimide, and adhesive strength can be maintained by an epoxy and an amine hardening | curing agent.
본 발명의 접착제용 수지 조성물에서, 상기 비스말레이미드 수지: 에폭시 수지= 5~95 중량부: 5~95 중량부일 수 있으며, 상기 아민 경화제는 상기 에폭시 수지에 대해 0.5~5 당량비로 포함될 수 있다. 에폭시 수지가 5 중량부 미만이면 접착 강도가 낮아질 수 있고, 반면 에폭시 수지가 95 중량부 초과이면 유연성과 내열성이 저하될 수 있다.In the resin composition for an adhesive of the present invention, the bismaleimide resin: epoxy resin = 5 to 95 parts by weight: may be 5 to 95 parts by weight, the amine curing agent may be included in a 0.5 to 5 equivalent ratio relative to the epoxy resin. If the epoxy resin is less than 5 parts by weight, the adhesive strength may be lowered, while if the epoxy resin is more than 95 parts by weight, flexibility and heat resistance may be lowered.
본 발명에서 비스말레이미드 수지는 특별히 한정되지 않고, 당업계에 알려진 통상의 것을 사용할 수 있다. 상기 비스말레이미드 수지의 예로는 4,4'-디페닐메탄 비스말레이미드(4,4'-diphenylmethane bismaleimide), m-페닐렌 비스말레이미드(m-phenylene bismaleimide), 비스페놀 A 디페닐 에테르 비스말레이미드(bisphenol A diphenyl ether bismaleimide), 3,3'-디메틸-5,5'-디에틸-4,4'-디페닐메탄 비스말레이미드(3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-메틸-1,3-페닐렌 비스말레이미드(4-methyl-1,3-phenylene bismaleimide), 1,1'-(3,3'-디메틸-1,1'-비페닐-4,4'-디일)비스말레이미드 (1,1'-(3,3'-dimethyl-1,1'-biphenyl-4,4'-diyl)bismaleimide 등이 있으나, 이에 한정되는 것은 아니다. 또한, 이들 비스말레이미드 수지는 단독 또는 2종 이상 혼합하여 사용될 수 있다.In the present invention, the bismaleimide resin is not particularly limited, and common ones known in the art may be used. Examples of the bismaleimide resin include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. Bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl- 4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide, 1,1 '-(3,3'-dimethyl-1, 1'-biphenyl-4,4'-diyl) bismaleimide (1,1 '-(3,3'-dimethyl-1,1'-biphenyl-4,4'-diyl) bismaleimide, etc. In addition, these bismaleimide resins can be used individually or in mixture of 2 or more types.
본 발명에서 에폭시 수지는 특별히 한정되지 않고, 당업계에 알려진 통상의 것을 사용할 수 있다. 상기 에폭시 수지의 비제한적인 예로는, 비스페놀계 에폭시 수지, BPA Free계 에폭시 수지, Brominated 에폭시 수지, 비스페놀 F형 에폭시 수지, 2관능기 이상의 다관능기 에폭시 수지, 노블락 에폭시 수지, 페놀 노블락계 에폭시 수지, 크레졸 노블락 에폭시 수지, 비페닐형 에폭시 수지, 테트라 메틸 비페 닐형 에폭시 수지, 비스페놀 노블락형 에폭시 수지, 트리페닐 메탄형 에폭시 수지, 테트라 페닐에탄형 에폭시 수지, 디시 클로펜타디엔 페놀 부가 반응형 에폭시 수지, 페놀 아랄킬형 에폭시 수지, 나프톨 노블락형 에폭시 수지, 나프톨 아라킬형 에폭시 수지, 나프톨 페놀 공축 노블락형 에폭시 수지, 나프톨 코레졸 공축 노블락형 에폭시 수지, 방향족 탄화수소 포름알데히드 수지 변성 페놀 수지형 에폭시 수지, 비페닐 노블락형 에폭시 수지 등이 있다. 상기 에폭시 수지는 단독 또는 2종 이상 혼합하여 사용될 수 있다.In the present invention, the epoxy resin is not particularly limited, and conventional ones known in the art may be used. Non-limiting examples of the epoxy resins include bisphenol-based epoxy resins, BPA-free epoxy resins, brominated epoxy resins, bisphenol F-type epoxy resins, bifunctional or higher polyfunctional epoxy resins, noblock epoxy resins, phenolic noblock-based epoxy resins, and cresols. Noblock Epoxy Resin, Biphenyl Epoxy Resin, Tetramethyl Biphenyl Epoxy Resin, Bisphenol Noble Epoxy Resin, Triphenyl Methane Epoxy Resin, Tetraphenylethane Epoxy Resin, Diclopentadiene Phenolic Reaction Epoxy Resin, Phenol Aral Kill type epoxy resin, naphthol noblock type epoxy resin, naphthol arachyl type epoxy resin, naphthol phenol coaxial noblock type epoxy resin, naphthol corresol coaxial noblock type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl noblock type epoxy resin Resins and the like. The epoxy resins may be used alone or in combination of two or more thereof.
본 발명에서 아민 경화제는 특별히 한정되지 않고 당업계에 알려진 통상의 것을 사용할 수 있으나, 방향족 아민 경화제가 바람직하다. 상기 방향족 아민 경화제의 예로는, 디아미노디페닐 술폰(DDS, diaminodiphenyl sulfone), 디아미노디페닐 메탄(DDM, diaminodiphenyl methane), 1,2-비스-(3-아미노-N-페녹시)벤젠(APBN, 1,2-bis-(3-amino-N-phenoxy)benzene, 3,3'-옥시디아닐린(3,3'-oxydianiline), 비스-(4-아미노-N-페닐)에테르)(MDA, bis-(4-amino-N-phenyl)ether), 옥시비스벤젠아민(oxybisbenzenamine), 디아미노 벤자닐라이드(diamino benzanilide), 메틸렌디아닐린(methylenedianiline) 등이 있으나, 이에 한정되는 것은 아니다. 또한, 상기 아민 경화제는 단독 또는 2종 이상 혼합하여 사용될 수 있다.In the present invention, the amine curing agent is not particularly limited and may be a conventional one known in the art, but an aromatic amine curing agent is preferable. Examples of the aromatic amine curing agent, diaminodiphenyl sulfone (DDS, diaminodiphenyl sulfone), diaminodiphenyl methane (DDM, diaminodiphenyl methane), 1,2-bis- (3-amino-N-phenoxy) benzene ( APBN, 1,2-bis- (3-amino-N-phenoxy) benzene, 3,3'-oxydianiline, bis- (4-amino-N-phenyl) ether) MDA, bis- (4-amino-N-phenyl) ether), oxybisbenzenamine, diamino benzanilide, methylenedianiline, and the like, but are not limited thereto. In addition, the amine curing agent may be used alone or in combination of two or more.
또한, 본 발명의 수지 조성물에는 1종 이상의 용매가 포함될 수 있다. 상기 용매는 비스말레이미드 및 에폭시 수지를 용해하는 것이라면 특별히 한정되지 않는다. 상기 용매의 비제한적인 예로는, 디메틸술폭시드, 디에틸술폭시드 등의 술폭시드계, N,N-디메틸포름아미드, N,N-디에틸포름아미드 등의 포름아미드계, N,N-디메 틸아세트아미드, N,N-디에틸아세트아미드 등의 아세트아미드계, N-메틸피롤리돈(NMP) 등의 피롤리돈계, 페놀, 크레졸, 크실레놀, 할로겐화페놀, 카테콜 등의 페놀계, 톨루엔, 크실렌 등의 방향족 탄화수소계, 헥사메틸포스포르아미드, γ-부티로락톤, 테트라히드로푸란, 1,4-디옥산, 모노그라임, 디옥솔란, 디메톡시에탄 등이 있다. 이들 용매는 단독 또는 2종 이상 혼합하여 사용될 수 있으며, 용매의 사용량은 특별히 제한되지 않는다.In addition, the resin composition of the present invention may contain one or more solvents. The solvent is not particularly limited as long as it dissolves bismaleimide and an epoxy resin. Non-limiting examples of the solvent include sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, formamides such as N, N-dimethylformamide, N, N-diethylformamide, and N, N-dimeth Acetamides such as acetylacetamide and N, N-diethylacetamide, pyrrolidones such as N-methylpyrrolidone (NMP), and phenols such as phenol, cresol, xylenol, halogenated phenol and catechol And aromatic hydrocarbons such as toluene and xylene, hexamethylphosphoramide, γ-butyrolactone, tetrahydrofuran, 1,4-dioxane, monolime, dioxolane, dimethoxyethane and the like. These solvents may be used alone or in combination of two or more, and the amount of the solvent is not particularly limited.
본 발명의 수지 조성물은 열가소성 수지를 추가로 포함할 수 있다. 상기 열가소성 수지는 고무계 수지 및 폴리이미드 수지로 이루어진 군에서 선택될 수 있다. The resin composition of the present invention may further include a thermoplastic resin. The thermoplastic resin may be selected from the group consisting of rubber-based resins and polyimide resins.
본 발명의 수지 조성물은 경화제 및/또는 경화촉진제를 추가로 포함할 수 있다. 또한, 상기 에폭시 수지 이외에도 열경화성 수지, 페놀 수지 및/또는 시아네이트 수지 등을 더 포함할 수도 있다.The resin composition of the present invention may further include a curing agent and / or a curing accelerator. In addition to the epoxy resin, a thermosetting resin, a phenol resin and / or a cyanate resin may be further included.
본 발명의 수지 조성물은 동박, 니켈박 등의 금속박, 캐리어박, 또는 합성수지 필름과의 접착성이 우수하므로 접착제 용도로 사용할 수 있다. Since the resin composition of this invention is excellent in adhesiveness with metal foil, such as copper foil and nickel foil, carrier foil, or a synthetic resin film, it can be used for an adhesive use.
또한, 본 발명의 수지 조성물은 용매에 대한 용해성이 좋기 때문에 사용시 가공성이 우수하다. 예를 들면, 본 발명의 수지 조성물을 용매로 용해시킨 수지 조성물 용액은 직접 시트상으로 형성한 상태 또는 바니시 상태로서 사용할 수 있다. 또한, 본 발명의 수지 조성물 용액은 이를 고체상으로 만든 후 적절하게 유기 용매에 용해하여 바니쉬로도 사용할 수 있다.In addition, since the resin composition of the present invention has good solubility in a solvent, it has excellent workability in use. For example, the resin composition solution which melt | dissolved the resin composition of this invention in the solvent can be used as the state formed directly in the sheet form, or as a varnish state. In addition, the resin composition solution of the present invention can be used as a varnish by making it into a solid phase and then appropriately dissolving it in an organic solvent.
본 발명의 수지 시트는 본 발명에 따른 접착제용 수지 조성물을 포함하는 것이 특징이다. 또한, 본 발명의 수지 시트는 지지체 상에 형성되는 수지 시트가 바람직하다. The resin sheet of this invention is characterized by including the resin composition for adhesive agents which concerns on this invention. In addition, the resin sheet of the present invention is preferably a resin sheet formed on a support.
본 발명의 수지 시트의 제조방법은 특별히 한정되지 않는다. 비제한적인 예를 들면, 본 발명에 따른 접착제용 수지 조성물을 1종 이상의 용매에 용해시킨 수지 조성물 용액을 각종 도포법에 의해 지지체 상에 형성하고, 건조시켜 얻을 수 있다. The manufacturing method of the resin sheet of this invention is not specifically limited. As a non-limiting example, the resin composition solution which melt | dissolved the resin composition for adhesive agents which concerns on this invention in 1 or more types of solvent can be formed on a support body by various application | coating methods, and can be obtained by drying.
상기 도포법은 특별히 제한되지 않고, 당업계에 알려진 통상의 방법이 사용될 수 있다. 비제한적인 예를 들면, 다이(Die) 코팅, 나이프 코팅, 그라비아 코팅, 립(Lip) 코팅, 롤(roll) 코팅, 콤마(comma) 코팅, 또는 이들의 혼합 방식 등 다양한 방식을 이용할 수 있다.The coating method is not particularly limited, and conventional methods known in the art may be used. For example and without limitation, various methods such as die coating, knife coating, gravure coating, lip coating, roll coating, comma coating, or a mixture thereof may be used.
상기 지지체는 도포, 건조 공정에서 필요한 내열성, 인쇄 회로 기판을 제조할 때 필요한 이형성을 갖는 것이면 특별히 한정되지 않는다. 상기 지지체의 비제한적인 예로는 금속박, 캐리어박, 또는 합성 수지 필름 등이 있다. 또한, 상기 금속박의 비제한적인 예로는 동박, 니켈박, 또는 알루미늄박 등이 있다.The support is not particularly limited as long as it has heat resistance required in the coating and drying steps and the releasability required when producing a printed circuit board. Non-limiting examples of the support include a metal foil, a carrier foil, or a synthetic resin film. Further, non-limiting examples of the metal foil include copper foil, nickel foil, aluminum foil and the like.
상기 지지체의 두께는 특별히 한정되지 않으며, 비제한적인 예로 금속박은 70㎛ 이하, 케리어박은 9㎛ 이하, 기타 박 및 필름은 100㎛ 이하일 수 있다. 또한, 상기 지지체는 양호한 회로 형상을 얻기 위해 표면 조도 Rz가 10㎛ 이하인 것이 바람직하다.The thickness of the support is not particularly limited. Non-limiting examples include metal foil of 70 μm or less, carrier foil of 9 μm or less, and other foils and films of 100 μm. It may be Moreover, it is preferable that surface roughness Rz is 10 micrometers or less in order to obtain the favorable circuit shape of the said support body.
또한, 본 발명의 수지 시트에는 표면의 오염, 흠집 등을 방지할 목적으로 보 호 필름을 설치할 수도 있다.The resin sheet of the present invention may also be provided with a protective film for the purpose of preventing surface contamination, scratches and the like.
본 발명의 수지 시트, 예를 들면 금속박의 지지체 상에 형성되는 수지 시트는 고절연 저항 및 양호한 접착 강도를 가지며 미세한 회로 형성이 가능하므로, 미세한 배선을 갖는 인쇄 회로 기판용 재료, 또는 빌드업 회로 기판용 재료로서 사용될 수 있다. Since the resin sheet of the present invention, for example, the resin sheet formed on the support of the metal foil, has high insulation resistance and good adhesive strength and can form fine circuits, a material for a printed circuit board having a fine wiring, or a buildup circuit board It can be used as a material.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[수지 조성물 제조][Resin composition preparation]
본 실시예 및 비교예의 수지 조성물 제조시, 비스말레이미드는 다이와카세이 산업(일본)의 BMI-1000, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5000, 또는 BMI-7000을 사용하였고; 에폭시 수지는 국도화학의 YD-011, YD-128, 다우 화학의 DER-383, DER-530, 또는 Dainippon ink and chemicla사의 HP-7200H를 사용하였다. 또한 아민 경화제는 와카야마 세이카 고교사의 TPE-R, TPE-Q, DETDA, DDS(Diaminodiphenyl sulfone), DDM(diaminodiphenyl methane), 또는 APBN(1,2-Bis-(3amino-N-Phenoxy)benzene)을 사용하였다.In preparing the resin compositions of this example and the comparative examples, the bismaleimide is BMI-1000, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5000, or BMI-7000 of Daiwa Kasei Industries (Japan). Was used; As the epoxy resin, YD-011, YD-128 of Kukdo Chemical, DER-383, DER-530 of Dow Chemical, or HP-7200H of Dainippon ink and chemicla was used. The amine curing agent also uses TPE-R, TPE-Q, DETDA, Diaminodiphenyl sulfone (DDS), diaminodiphenyl methane (DDM), or APBN (1,2-Bis- (3 amino-N-Phenoxy) benzene) from Wakayama Seikagyo Co., Ltd. It was.
(실시예 1~17) 수지 조성물(Examples 1-17) Resin Composition
비스말레이미드 수지는 고형분 중량비로 30중량%가 되도록 용매 DMF(dimethyformamide)에 용해하여 사용하였고, 아민 경화제는 고형분 중량비로 50 중량%가 되도록 용매 DMF에 용해하여 사용하였다.Bismaleimide resin was used by dissolving in solvent DMF (dimethyformamide) to be 30% by weight by weight of solids, and amine curing agent was used by dissolving in solvent DMF to be 50% by weight by weight of solids.
이후, 하기 표 1과 같이 비스말레이미드, 에폭시 수지 및 아민 경화제의 종류를 다르게 사용하여 수지 조성물을 제조하였다. Thereafter, the resin composition was prepared using different types of bismaleimide, an epoxy resin, and an amine curing agent as shown in Table 1 below.
하기 표 1의 실시예 1 내지 실시예 15의 경우, 고형분 중량비로 비스말레이미드는 40중량%, 에폭시 수지는 25중량%, 아민 경화제는 35중량%가 되도록 혼합하고, 용매 대비 총 고형분의 중량비가 35중량%가 되도록 DMF를 투입한 후, 상온에서 최소 5시간 이상 혼합하여 수지 조성물을 제조하였다.In Examples 1 to 15 of Table 1, the bismaleimide is 40% by weight, the epoxy resin 25% by weight, the amine curing agent is mixed so that the 35% by weight, the weight ratio of total solids to solvent After the DMF was added so as to be 35% by weight, a resin composition was prepared by mixing at least 5 hours at room temperature.
또한, 하기 표 1의 실시예 16 및 실시예 17의 경우, 고형분 중량비로 비스말레이미드는 32중량%, 에폭시 수지는 20중량%, 아민 경화제는 28중량%, PI(실시예 16) 또는 NBR(실시예 17)는 20중량%가 되도록 혼합하고, 용매 대비 총 고형분의 중량비가 35중량%가 되도록 DMF를 투입한 후, 상온에서 최소 5시간 이상 혼합하여 수지 조성물을 제조하였다. 이때 사용한 PI수지는 BPDA(3,3',4,4'-Biphenyltetracarboxylic acid dianhydride) 계열의 자체 합성한 수지를 사용하였고, NBR(Acrylo Nitrile Butadiene)은 1072계 NBR(금호석유화학의 KNB25H)을 사용하였다.In addition, in Examples 16 and 17 of Table 1, the bismaleimide is 32% by weight, 20% by weight epoxy resin, 28% by weight amine curing agent, PI (Example 16) or NBR (by weight of solids) Example 17) was mixed to 20% by weight, DMF was added so that the weight ratio of total solids to solvent is 35% by weight, and then mixed at room temperature for at least 5 hours to prepare a resin composition. The PI resin used was BPDA (3,3 ', 4,4'-Biphenyltetracarboxylic acid dianhydride) series self-synthesized resin, and NBR (Acrylo Nitrile Butadiene) uses 1072 NBR (KNB25H from Kumho Petrochemical). It was.
(비교예 1~10) 수지 조성물 제조(Comparative Examples 1-10) Resin Composition Preparation
하기 표 1과 같은 조성비에 따른 것을 제외하고는 실시예 1 내지 실시예 17과 동일한 방법으로 수지 조성물을 제조하였다.A resin composition was prepared in the same manner as in Example 1 to Example 17, except that the composition ratio was as shown in Table 1 below.
이때, 비교예 2 및 비교예 3의 경우, 에폭시 수지 및 아민 경화제는 고형분 중량비가 각각 70중량%와 30중량%가 되도록 혼합하고, 용매 대비 총 고형분의 중량 비가 35중량%가 되도록 DMF를 투입하였다.In this case, in the case of Comparative Example 2 and Comparative Example 3, the epoxy resin and the amine curing agent were mixed so that the solid weight ratio was 70 wt% and 30 wt%, respectively, and DMF was added so that the weight ratio of the total solids to the solvent was 35 wt%. .
또한, 비교예 4의 경우 비스말레이미드 및 아민 경화제는 고형분 중량비로 각각 70중량%와 30중량%가 되도록 혼합하고, 용매 대비 총 고형분의 중량비가 35중량%가 되도록 DMF를 투입하였다.In addition, in the case of Comparative Example 4, the bismaleimide and the amine curing agent were mixed so as to be 70 wt% and 30 wt%, respectively, in the solid weight ratio, and DMF was added so that the weight ratio of the total solids to the solvent was 35 wt%.
또한, 비교예 6 및 비교예 7에서 경화제는 각각 DETA(Diethyl methylbenzamide), TETA(Triethylene tetramine)를 사용하였다.In addition, in Comparative Example 6 and Comparative Example 7, a curing agent used DETA (Diethyl methylbenzamide), TETA (Triethylene tetramine), respectively.
[수지 시트 제조][Resin Sheet Manufacturing]
(수지 시트의 제조예 1~17) (Manufacture example 1-17 of resin sheet)
동박의 Shniy면 또는 Mitsui VLP (Rz=3㎛)의 Matte면에 실시예 1 내지 실시예 17에서 제조한 수지 조성물을 각각 코팅하고, 180℃에서 10분간 건조하여 5㎛의 두께로 접착제층이 형성된 수지 시트를 제조하였다.The resin composition prepared in Examples 1 to 17 was coated on the Shniy side of the copper foil or the Matte side of Mitsui VLP (Rz = 3 μm), respectively, and dried at 180 ° C. for 10 minutes to form an adhesive layer having a thickness of 5 μm. A resin sheet was produced.
(비교 제조예 1~10) 수지 시트 제조(Comparative Production Examples 1 to 10) Resin Sheet Production
실시예 1 내지 실시예 17에서 제조한 수지 조성물 대신 비교예 1 내지 비교예 10에서 제조한 수지 조성물을 각각 사용한 것을 제외하고는, 수지 시트의 제조예 1~17과 동일한 방법으로 접착제층이 형성된 수지 시트를 제조하였다.Resin in which an adhesive bond layer was formed by the method similar to manufacture example 1-17 of a resin sheet except having used the resin composition manufactured by comparative example 1 thru | or comparative example 10 instead of the resin composition prepared in Examples 1-17. Sheets were prepared.
[실험예: 접착 강도 및 내열성 측정]Experimental Example: Measurement of Adhesive Strength and Heat Resistance
수지 시트의 제조예 1~17 및 비교 제조예 1~10에서 제조한 접착제층이 형성된 수지 시트 각각을 두산전자 7049 HF Prepreg에 적층하고, 온도 220℃에서 1시간 30분간 Press하여 동박 적층판을 제작하였다. Each of the resin sheets on which the adhesive layers prepared in Production Examples 1 to 17 and Comparative Production Examples 1 to 10 of the resin sheet were formed was laminated on Doosan Electronics 7049 HF Prepreg, and pressed at a temperature of 220 ° C. for 1 hour and 30 minutes to produce a copper foil laminate. .
접착제층의 특성을 분석하기 위하여 Peel Strength를 측정하였고, 또한 288℃에서 Solder floating하여 내열성을 분석하였다. 그리고, 그 결과를 하기 표 1에 기재하였다.Peel strength was measured to analyze the properties of the adhesive layer, and also heat resistance was analyzed by solder floating at 288 ° C. The results are shown in Table 1 below.
위의 표 1의 결과로부터, 비교예의 수지 조성물을 사용한 경우보다 실시예 1~17의 수지 조성물을 사용한 경우, 접착제층의 접착 강도가 동박의 Shniy면 또는 Mitsui VLP (Rz=3㎛)의 Matte면 모두에서 크게 향상되었으며, 내열성 또한 향상되었음을 알 수 있었다.From the results of Table 1 above, when the resin composition of Examples 1 to 17 was used than when the resin composition of the comparative example was used, the adhesive strength of the adhesive layer was the Shniy side of the copper foil or the Matte side of Mitsui VLP (Rz = 3 μm). In all, it was greatly improved, and the heat resistance was also improved.
이상을 통해 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명 및 첨부한 도면의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.
Claims (12)
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| KR1020070139658A Ceased KR20090071774A (en) | 2007-12-28 | 2007-12-28 | Resin composition for adhesives and use thereof |
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| JP2016204420A (en) * | 2015-04-15 | 2016-12-08 | 京セラ株式会社 | Epoxy resin molding material for sealing and electronic parts |
| WO2019117624A1 (en) * | 2017-12-14 | 2019-06-20 | 주식회사 엘지화학 | Thermosetting resin composition for coating thin metal film, and metal laminate using same |
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| CN111372997B (en) * | 2018-04-10 | 2022-12-09 | 株式会社Lg化学 | Thermosetting resin composite material for metal clad laminate and metal clad laminate using same |
| US12091510B2 (en) | 2018-04-10 | 2024-09-17 | Lg Chem, Ltd. | Thermosetting resin composite and metal clad laminate using the same |
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| WO2020060197A1 (en) * | 2018-09-20 | 2020-03-26 | 주식회사 엘지화학 | Thermocurable resin composition for coating metal thin film, resin-coated metal thin film using same, and metal foil laminate |
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