KR100306254B1 - An electrically conductive Ag paste composition - Google Patents
An electrically conductive Ag paste composition Download PDFInfo
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- KR100306254B1 KR100306254B1 KR1019990010010A KR19990010010A KR100306254B1 KR 100306254 B1 KR100306254 B1 KR 100306254B1 KR 1019990010010 A KR1019990010010 A KR 1019990010010A KR 19990010010 A KR19990010010 A KR 19990010010A KR 100306254 B1 KR100306254 B1 KR 100306254B1
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- resin
- silver paste
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- 239000000203 mixture Substances 0.000 title claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-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
- -1 diamide Aromatic amines Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008240 homogeneous mixture Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
Abstract
본 발명은 프린트 회로 기판에 있는 쓰루홀(through hole) 부분의 신뢰성이 우수한 도전성 은 페이스트 조성물에 관한 것이며, 더욱 상세하게는 바인다로 분자량이 5,000∼10,000인 하기 일반식 (Ⅰ)의 레졸형 고분자 페놀수지와 열경화성 또는 열가소성계 고분자를 함유하여 쓰루홀 부분에 양호한 도전성을 부여하고, 경시변화에 따른 쓰루홀 부분의 도전성 불량을 일으키지 않는 도전성 은 페이스트 조성물에 관한 것이다.The present invention relates to a conductive silver paste composition having excellent reliability of a through hole portion in a printed circuit board, and more particularly, to a resol-type polymer phenol of formula (I) having a molecular weight of 5,000 to 10,000 Containing a resin and a thermosetting or thermoplastic polymer to impart good conductivity to the through hole portion, and relates to a conductive silver paste composition that does not cause poor conductivity of the through hole portion due to changes over time.
식중, n은 10이고, m은 0.1∼0.9이다.In formula, n is 10 and m is 0.1-0.9.
Description
본 발명은 프린트 회로 기판에 있는 쓰루홀(through hole) 부분의 신뢰성이 우수한 도전성 은 페이스트 조성물에 관한 것이며, 더욱 상세하게는 바인다로 분자량이 5,000∼10,000인 하기 일반식 (Ⅰ)의 레졸형 고분자 페놀수지와 열경화성 또는 열가소성계 고분자를 함유하여 쓰루홀 부분에 양호한 도전성을 부여하고, 경시변화에 따른 쓰루홀 부분의 도전성 불량을 일으키지 않는 도전성 은 페이스트 조성물에 관한 것이다.The present invention relates to a conductive silver paste composition having excellent reliability of a through hole portion in a printed circuit board, and more particularly, to a resol-type polymer phenol of formula (I) having a molecular weight of 5,000 to 10,000 Containing a resin and a thermosetting or thermoplastic polymer to impart good conductivity to the through hole portion, and relates to a conductive silver paste composition that does not cause poor conductivity of the through hole portion due to changes over time.
[화학식 1](Ⅰ)[Formula 1] (Ⅰ)
식중, n은 10이고, m은 0.1∼0.9이다.In formula, n is 10 and m is 0.1-0.9.
종이 페놀수지 기판 또는 유리기재 에폭시 수지 기판 등의 프린트 회로기판의 양면회로를 도통(導通)시키는 방법으로서 쓰루홀이 행해지고 있는데, 과거에는통상 기판에 드릴로 구멍을 뚫고 구멍에 도금을 행하여 양면을 도통시키는 도금법이 일반적으로 사용되었다. 그러나, 도금공정은 조작이 복잡하며, 게다가 도금액의 처리가 환경문제로 대두되면서, 이에 대한 대체 방법으로써 원가절감 효과가 크고 환경 친화적인 은 쓰루홀이 개발되면서 점차 그 응용 및 적용분야가 확대되고 있다.Through-holes are used as a method of conducting double-sided circuits of printed circuit boards, such as paper phenolic resin substrates or glass-based epoxy resin substrates. In the past, through-holes are usually drilled and plated into holes to conduct both surfaces. Plating method was generally used. However, as the plating process is complicated to operate, and the treatment of the plating solution has become an environmental problem, the application and application fields of the plating process have been gradually expanded with the development of a cost-effective and environmentally friendly silver through hole as an alternative method. .
은 쓰루홀은 프린트 회로기판의 랜드부에 쓰루홀을 설계하고, 여기에 도전성 은 페이스트(이하, '은 페이스트'라 한다)를 사용하여 홀을 메꾼 후, 가열·경화시켜 양면을 도통시킨 프린트 배선기판을 제조하는 방법으로, 홀내에 은 페이스트를 충진시키는 방법으로는 바늘에 은 페이스트를 묻혀 구멍안을 상하 이동시키는 방법이 있는데, 최근에는 인쇄기술의 발달로 스크린 인쇄법에 의한 충진이 일반적으로 행해지고 있다.Silver through-holes design through-holes on lands of printed circuit boards, filled with holes using conductive silver paste (hereinafter referred to as silver paste), and then printed and wired on both sides by heating and curing. As a method of manufacturing a substrate, a method of filling a silver paste into a hole is a method of applying a silver paste to a needle and moving the hole up and down. Recently, screen printing has been generally performed due to the development of printing technology. .
이러한 은 쓰루홀에 사용되는 은 페이스트로는 은분 또는 은분과 기타 금속분말, 예를 들면 구리, 아연, 금, 백금, 니켈 등을 혼용 및 피복시킨 도전분말에 바인다로서 열경화형 수지 또는 열가소성 수지를 혼용한 조성물이 알려져 있다.The silver paste used in the silver through hole is mixed with a silver powder or a conductive powder coated with silver and other metal powders such as copper, zinc, gold, platinum, nickel, and the like as a thermosetting resin or a thermoplastic resin. One composition is known.
그러나, 종래의 은 페이스트를 이용한 경우에는 부품실장시킨 프린트 배선판의 신뢰성 측면에서 문제가 있다. 특히, 프린트 배선판의 쓰루홀 부분의 두께 방향 또는 평행방향 크랙이 생겨 도통 불량이 자주 발생하는 문제점이 있다. 따라서, 최근에는 고밀도 실장된 프린트 배선판의 신뢰성이 강조되고 있으며, 예를 들면, 고온 및 저온 방치, 항온항습, 냉열충격시험, 가압시험, 내열성 및 내약품성 시험 등 13가지의 기본 신뢰성 테스트를 하여, 시험 전후에 저항변화가 적고 마이그레이션의 발생이 없는 높은 신뢰성의 도전성 페이스트가 요구되고 있다.However, in the case of using a conventional silver paste, there is a problem in terms of reliability of the printed wiring board mounted with components. In particular, there is a problem that poor conduction occurs frequently due to cracks in the thickness direction or parallel direction of the through-hole portion of the printed wiring board. Therefore, in recent years, the reliability of high density mounted printed wiring boards has been emphasized, and for example, 13 basic reliability tests such as high temperature and low temperature standing, constant temperature and humidity, cold shock test, pressurization test, heat resistance and chemical resistance test, There is a demand for a highly reliable conductive paste with little resistance change before and after the test and without migration.
따라서, 본 발명자들은 높은 신뢰성의 도전성 은 페이스트를 제공하기 위해서 연구를 하게 되었다.Therefore, the present inventors have made an effort to provide a highly reliable conductive silver paste.
그 결과, 스루홀에서의 내부공동 및 크랙은 경화시의 용제의 증발 및 바인다의 경화수축 뿐만 아니라 은페이스트의 유동특성과 홀내의 은 페이스트의 부착상태에 영향을 받는다는 것을 알게 되었고, 이에 은 페이스트의 바인다로 유연성을 부여한 고분자 페놀수지를 사용하면 경화수축시 발생하는 내부응력에 대응할 수 있고, 쓰루홀내의 은 페이스트 부착 및 유동특성을 우수하게 할 수 있어 쓰루홀의 신뢰성을 향상시킬 수 있다는 것을 발견하고 본 발명을 완성하게 되었다.As a result, it was found that the internal cavities and cracks in the through hole are affected by the flow characteristics of the silver paste and the adhesion state of the silver paste in the hole as well as the evaporation of the solvent during curing and the hardening shrinkage of the binder. It was found that the use of a high-molecular phenolic resin, which provides flexibility as a binder, can cope with internal stresses generated during curing shrinkage, and can improve silver paste adhesion and flow characteristics in through-holes, thereby improving the reliability of through-holes. The invention was completed.
따라서, 본 발명의 목적은 프린트 회로 기판에 있는 쓰루홀(through hole) 부분의 신뢰성이 우수한 도전성 은 페이스트 조성물을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a conductive silver paste composition with excellent reliability of through hole portions in a printed circuit board.
상기한 목적을 달성하기 위하여, 본 발명의 은 페이스트 조성물은 바인다로서 분자량이 5,000∼10,000인 하기 일반식 (Ⅰ)의 고분자 페놀 수지와, 열가소성 수지 또는 열경화성 수지를 100:10∼70의 범위로 혼합한 것을 사용함을 특징으로 한다.In order to achieve the above object, the silver paste composition of the present invention is a binder, the polymer phenol resin of the following general formula (I) having a molecular weight of 5,000 to 10,000 and a thermoplastic resin or a thermosetting resin are mixed in the range of 100: 10 to 70 It is characterized by using one.
[화학식 1](Ⅰ)[Formula 1] (Ⅰ)
식중, n은 10이고, m은 0.1∼0.9이다.In formula, n is 10 and m is 0.1-0.9.
이하 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
일반적인 은 페이스트 조성물의 경우 바인다로서 에폭시 수지, 페놀수지, 포화 폴리에스테르수지, 불포화 폴리에스테르수지, 폴리이미드 수지, 폴리아마이드수지, 아크릴 수지 등과 같은 열경화성 수지 또는 열가소성 수지를 1종 이상을 혼합하여 사용하여 왔다. 그러나, 이러한 수지를 은 페이스트 조성물의 바인다로 사용할 경우 쓰루홀내에 크랙이나 공동이 심하여 홀당 저항이 높고 신뢰성이 낮은 단점이 있다. 따라서, 본 발명에서는 상기한 열가소성 또는 열경화성 수지와 함께 유연성 관능기를 갖으며, 분자량이 5,000∼10,000인 하기 일반식 (Ⅰ)의 고분자 페놀수지를 혼합 사용한다.As a general silver paste composition, one or more thermosetting resins or thermoplastic resins such as epoxy resins, phenol resins, saturated polyester resins, unsaturated polyester resins, polyimide resins, polyamide resins, acrylic resins, etc. come. However, when the resin is used as a binder of the silver paste composition, cracks or cavities are severe in the through holes, and thus, there is a disadvantage in that the resistance per hole is high and the reliability is low. Therefore, in this invention, the high molecular weight phenol resin of the following general formula (I) which has a flexible functional group and molecular weight is 5,000-10,000 with the above thermoplastic or thermosetting resin is mixed and used.
[화학식 1](Ⅰ)[Formula 1] (Ⅰ)
식중, n은 10이고, m은 0.1∼0.9이다.본 발명의 고분자 수지의 제조방법에 대한 구체적인 설명 및 반응공정도는 다음과 같다;(1) 페놀수지와 산성촉매를 부가한 후, 여기에 1,10-데칸디올 0.1~0.9mol을 부가하여 반응시키는 단계; (2) 상기 (1)을 중화시킨 후, 용매와 염기성 촉매를 부가하고, p-포름알데히드를 부가하여 반응시키는 단계; (3)용매 및 미반응 반응물을 제거하여 고분자 페놀수지를 얻는 단계.여기서 산성 촉매는 스테아르산, 시트르산, 옥살산, 술폰산 및 p-톨루엔술폰산 등을 사용할 수 있고, 용매로는 크실렌, 톨루엔, 벤젠을 사용할 수 있으며, 염기성 촉매로는 벤젠디메틸아민, 트리부틸아민, 트리에틸아민, 트리페닐포스핀 등을 사용할 수 있다. In the formula, n is 10 and m is 0.1 to 0.9. The detailed description of the method for producing the polymer resin and the reaction process diagram are as follows: (1) After adding phenol resin and acid catalyst, Reacting by adding 0.1-0.9 mol of 10-decanediol; (2) neutralizing the above (1), adding a solvent and a basic catalyst and reacting by adding p-formaldehyde; (3) removing the solvent and the unreacted reactant to obtain a high molecular weight phenol resin, wherein the acid catalyst may be stearic acid, citric acid, oxalic acid, sulfonic acid and p-toluenesulfonic acid, and the like. As the basic catalyst, benzenedimethylamine, tributylamine, triethylamine, triphenylphosphine and the like can be used.
상기한 방법에 의해 제조되는 본 발명의 고분자 페놀수지와 열가소성 또는 열경화성 수지의 비율을 100:10∼70이 되도록 혼합함으로써 본 발명의 도전성 은 페이스트 조성물을 제조할 수 있다. 즉, 혼합비율에 따라 유연성, 홀내 형상성 등의 물성이 달라지기 때문에, 상기한 범위로 혼합하는 것이 바람직하다.The electrically conductive silver paste composition of this invention can be manufactured by mixing the ratio of the high molecular phenol resin and thermoplastic or thermosetting resin of this invention manufactured by said method so that it may become 100: 10-70. That is, since physical properties, such as flexibility and an in-hole shape, change with a mixing ratio, it is preferable to mix in said range.
바인다의 사용량은 통상적인 은 페이스트 조성물에서 바인다가 사용되는 양, 즉, 은 분말 총 중량에 대하여 10∼60중량%의 양으로 당업자가 적의하게 선정할 수 있다.The amount of binder used may be appropriately selected by those skilled in the art in the amount of binder used in conventional silver paste compositions, that is, in an amount of 10 to 60% by weight based on the total weight of silver powder.
본 발명의 은 페이스트 조성물에서 은 분말로는 은 분말 자체를 사용할 수 있지만, 성능에 큰 영향을 미치지 않는 한 다른 금속분말, 예를 들면 구리, 아연, 백금, 금, 니켈 등의 전도성 금속을 약 2∼3%이하의 양으로 혼용한 것을 사용할 수 있다. 한편, 은 분말은 그 형상을 특별히 한정하는 것은 아니지만, 인편상 또는 수지상의 은 분말을 사용하는 것이 바람직하다. 인편상 은 분말이란 SEM에 의해 결정된 것처럼 주 모양이 인편상인 것으로, 입자의 크기는 평균 1∼30㎛인 것으로, 약 0.8∼1.4㎡/g의 표면적과 99%이상의 순도를 갖는다. 은 분말의 사용량은 통상적인 은 페이스트 조성물에서 은 분말이 사용되는 양, 즉 조성물 총 중량에 대하여 50∼60중량%의 양으로 당업자가 적의하게 선정할 수 있다.In the silver paste composition of the present invention, silver powder itself may be used as the silver powder, but other metal powders such as copper, zinc, platinum, gold, nickel and the like may be used as long as they do not significantly affect performance. The thing mixed in quantity of -3% or less can be used. On the other hand, silver powder does not specifically limit the shape, It is preferable to use a flaky or dendritic silver powder. The flaky silver powder is flaky in its main shape, as determined by SEM, and has an average particle size of 1 to 30 µm, a surface area of about 0.8 to 1.4 m 2 / g, and a purity of 99% or more. The amount of the silver powder to be used may be appropriately selected by those skilled in the art in the amount of the silver powder used in the conventional silver paste composition, that is, 50 to 60% by weight based on the total weight of the composition.
경화제는 경화조건, 경화시간, 및 저장안정성 등을 고려하여 사용되는 수지에 적합한 것을 선택하여 사용하는데, 예를 들면 디시안아미드, 카르복실산히드라지드 등과 같은 아민계, 3-(3,4-디클로로페닐)-1,1-디메틸 우레아와 같은 우레아계, 프탈릭산무수물, 메티나딘산 무수물(methynadic anhydride), 피로멜틴산 무수물(phyromelltic acid anhydride), 헥사히드로프탈릭산과 같은 무수물계, 디아미드디페닐메탄, 디아미드디페닐술폰산과 같은 방향족 아민계등이 있다. 경화제의 사용량은 통상적인 은 페이스트 조성물에서 경화제가 사용되는 양으로 당업자가 적의하게 선정할 수 있다.The curing agent is selected and used for the resin used in consideration of the curing conditions, curing time, and storage stability, for example, amine-based, such as dicyanamide, carboxylic acid hydrazide, 3- (3,4- Ureas such as dichlorophenyl) -1,1-dimethyl urea, phthalic anhydride, methydic anhydride, phyromelltic acid anhydride, anhydrides such as hexahydrophthalic acid, diamide Aromatic amines such as diphenylmethane and diamide diphenylsulfonic acid. The amount of the curing agent used may be appropriately selected by those skilled in the art in the amount of the curing agent used in the conventional silver paste composition.
용제로는 예를 들면 셀룰로오스계, 카르비톨계, 테르펜올, 시클로헥산온, 이소포론 등과 같은 일반 범용용제를 1종 또는 2종 이상 혼용하여 사용할 수 있는데, 인쇄시의 작업성을 고려하여 150∼200℃에서 끓는점을 갖는 용제를 사용하는 것이 바람직하다. 사용량은 조성물 총 중량에 대하여 10∼50중량%의 양으로 사용하는 것이 바람직하다.As a solvent, for example, one or two or more general-purpose solvents such as cellulose, carbitol, terpenol, cyclohexanone, and isophorone may be used. It is preferable to use a solvent having a boiling point at 200 ° C. The amount used is preferably used in an amount of 10 to 50% by weight based on the total weight of the composition.
분산제로는 고지방산의 에틸렌옥사이드, 프로필렌옥사이드 부가 에스테르 화합물, 소르비탄 지방산 에스테르 화합물, 고급알톨 술폰산 에스테르 알카리염, 인산 화합물 등 비이온성 분산제를 사용한다.As the dispersant, nonionic dispersants such as high fatty acid ethylene oxide, propylene oxide addition ester compound, sorbitan fatty acid ester compound, higher altol sulfonic acid ester alkali salt and phosphoric acid compound are used.
그 밖에 요변제, 침강방지제, 산화 방지제, 부식억제제, 활제 등 요구물성에 따라 다양한 첨가물이 단독 또는 복합적으로 사용될 수 있다.In addition, various additives may be used alone or in combination depending on the required properties such as thixotropic agents, anti-settling agents, antioxidants, corrosion inhibitors, lubricants.
이하, 실시예 및 시험예를 들어 본 발명을 상세히 설명하지만, 본 발명이 이들예로만 한정되는 것은 아니다.[제조예]본 발명의 고분자 페놀수지의 제조예는 다음과 같다.① 반응기를 45℃로 예열한 상태에서 페놀수지(덕산화학(주), 분자량 100.07) 1mol에 산성촉매로 술폰산을 2.0phr을 투입하였다.② 여기에 1,10-데칸디올(알드리치사, 분자량 174.28)을 0.2mol 투입하고, 120℃에서 6시간 반응시켰다.③ 이후, 온도를 40~50℃로 낮추고, 암모니아 워터를 사용하여 중화시킨 후, 벤젠을 용매로 하고, 염기성 촉매로 트리에틸아민을 2.0phr을 첨가한 후. p-포름알데히드(알드리치사)를 1.2mol 투입하여 95℃에서 12~13시간 반응시켰다.④ 반응후 온도를 120℃로 승온하며, 서서히 감압(0.1atm)하여 용매 및 미 반응물을 제거한 후, 부틸셀로솔브로 냉각종결함으로써 최종 생성물을 얻었다.참고로, 상기와 같이 제조된 본 발명의 고분자 페놀수지의 시험결과 분석 데이타는 다음과 같다.
상기 일반식 (Ⅰ)의 본 발명의 고분자 페놀수지(n=10, m=0.2) 25g과 비스페놀 A형 에폭시 수지 YD-011(국도화학제, EEQ 450-500) 25g을 일반 믹서기에서 혼합한 후, 부틸셀로솔브아세테이트 용액 30g을 넣어 잘 혼합하였다. 그 다음, 아민계 경화제인 디시안아미드 5g과 인편상 은분 100g을 넣고 균일 조성물이 될 때까지 충분히 교반하였다. 균일한 혼합물이 얻어지면 3-롤밀로 약 30㎛이하의 입도가 되도록 분산시켰다.After mixing 25 g of the polymer phenol resin (n = 10, m = 0.2) of the present invention of general formula (I) and 25 g of bisphenol A type epoxy resin YD-011 (manufactured by Kukdo Chemical, EEQ 450-500) in a general mixer 30 g of butyl cellosolve acetate solution was added and mixed well. Then, 5 g of dicyanamide, which is an amine curing agent, and 100 g of flaky silver powder were added thereto, and the mixture was sufficiently stirred until a uniform composition was obtained. Once a homogeneous mixture was obtained, the mixture was dispersed with a 3-roll mill to a particle size of about 30 μm or less.
이렇게 얻어진 조성물은 적정 점도 조정을 한 후 스크린 인쇄로 테스트 기판(Glass Modified Epoxy 수지 적층판)에 도포한다. 일단 기재에 도포하고 나면, 온도를 상승시켜가며 건조·경화시켜 최종 도막물을 얻었다. 건조·경화는 일반 대류식 열풍건조 오븐에서 행해졌고, 보통 80℃에서 30분, 150℃에서 30분 행하였다. 이렇게 얻은 최종 도막물의 체적저항, 홀 저항, 밀착력, 유연성, 홀 형상성, 신뢰성을 하기 방법으로 평가하였다.The composition thus obtained is applied to a test substrate (Glass Modified Epoxy Resin Laminate) by screen printing after adjusting the appropriate viscosity. Once applied to the substrate, the final coating film was obtained by drying and curing with increasing the temperature. The drying and curing were performed in a general convection hot air drying oven, and were usually performed at 80 ° C for 30 minutes and at 150 ° C for 30 minutes. The volume resistance, hole resistance, adhesion, flexibility, hole shape, and reliability of the final coated film thus obtained were evaluated by the following method.
1) 도전성1) conductivity
·체적저항: 최종 도막물의 양 끝에 전압단자를 대고 오옴메터(ohm meter)로 저항을 측정한 후, 하기식에 따라 계산하였다.Volume resistance: The resistance was measured by an ohm meter with a voltage terminal at both ends of the final coating material, and then calculated according to the following equation.
ρ[Ω·㎝]=(측정 저항×전극의 폭×도막의 두께)/전극의 길이ρ [Ω · cm] = (measurement resistance x electrode width x coating film thickness) / electrode length
·홀 저항: 양쪽의 구리 측정단자 사이에 홀이 있는 테스트 쿠폰에 상기에서 얻은 조성물을 인쇄·경화시킨 후, 구리측정단자를 통해 저항을 측정하고, 홀수로 나눈다.Hall resistance: After printing and hardening the composition obtained above to the test coupon with a hole between both copper measuring terminals, resistance is measured through a copper measuring terminal and divided by odd number.
2) 유연성(erichsen test): DIN ISO 1520(1973년)으로 측정하였다.2) Erichsen test: measured according to DIN ISO 1520 (1973).
3) 밀착력(Cross-cut tape test): 도막물위에 셀로판 테이프를 붙어 90°의 각도로 잡아당겼을 때, 박리의 정도를 하기의 기준으로 평가하였다.3) Cross-cut tape test: When the cellophane tape was attached to the coating material and pulled at an angle of 90 °, the degree of peeling was evaluated based on the following criteria.
◎: 매우 좋음, ○: 좋음, △: 좋지 낳음, ×: 매우 나쁨◎: very good, ○: good, △: good birth, ×: very bad
4) 홀내형상성 : 홀의 절단면을 촬영하여 다음의 평가기준으로 평가하였다.4) Hole shape: The cut surface of the hole was photographed and evaluated according to the following evaluation criteria.
◎: 내부에 틈(void)이 없고, 내벽의 두께가 균일함.(Double-circle): There are no voids inside, and the thickness of an inner wall is uniform.
○: 내부에 틈은 없으나 내벽의 균일성이 부족함.(Circle): There is no gap inside but lacks uniformity of inner wall.
△: 미세한 틈이 있고, 내벽의 균일성이 부족함.(Triangle | delta): There exists a minute gap and the uniformity of an inner wall is lacking.
×: 내부에 틈이 많고, 내벽의 균일성도 없음.X: There are many gaps inside, and there is no uniformity of an inner wall.
5) 신뢰성5) reliability
·고온방치: 100℃, 1,000HRs의 조건하에 방치하였을 때, 시험전후 S.T.H 저항변화율이 ±100%이하이고, 시험완료후 S.T.H 저항이 200mΩ이하/hole당 외관에 이상이 없는 경우 합격이다.High temperature: When it is left under the condition of 100 ℃ and 1,000HRs, the S.T.H resistance change rate is less than ± 100% before and after the test, and the S.T.H resistance is less than 200mΩ / hole after completion of the test.
·냉열충격: -65℃에서 30분동안 유지하고, 125℃에서 30분 동안 유지하는 것을 100회 반복하였을 때, 시험전후 S.T.H 저항변화율이 ±100%이하이고, 시험완료후 S.T.H 저항이 200mΩ이하/hole당 외관에 이상이 없는 경우 합격이다.Cold shock: STH resistance change rate is ± 100% or less before and after the test when it is maintained for 30 minutes at -65 ° C and 30 minutes at 125 ° C, and the STH resistance is 200mΩ or less after completion of the test. Passed when there is no abnormality in appearance per hole.
·PCT: 121℃, 95% 상대습도(2ATM), 8HRs(불포화형)에서 유지하였을 때, 시험전후 S.T.H 저항변화율이 ±100%이하이고, 시험완료후 S.T.H 저항이 200mΩ이하/hole당 외관에 이상이 없는 경우 합격이다.PCT: When maintained at 121 ° C, 95% relative humidity (2ATM), and 8HRs (unsaturated), the STH resistance change rate is less than ± 100% before and after the test, and the STH resistance is less than 200mΩ / hole after the completion of the test. If there is no pass.
<실시예 2><Example 2>
실시예 1과 동일한 본 발명의 고분자 페놀수지 30g과 비스페놀 A형 에폭시 수지 YD-017(국도화학제, EEQ 1750-2100) 20g을 일반 믹서기에서 혼합한 후, 부틸셀로솔브아세테이트 용액 30g을 넣어 잘 혼합하였다. 그 다음, 아민계 경화제인 디시안아미드 3g과 인편상 은분 100g을 넣고 균일 조성물이 될 때까지 충분히 교반하였다. 균일한 혼합물이 얻어지면 3-롤밀로 약 30㎛이하의 입도가 되도록 분산시켰다.30 g of the high-molecular-weight phenolic resin of the present invention same as Example 1 and 20 g of bisphenol A epoxy resin YD-017 (manufactured by Kukdo Chemical Co., Ltd., EEQ 1750-2100) were mixed in a general mixer, and then 30 g of butyl cellosolve acetate solution was added. Mixed. Then, 3 g of dicyanamide, an amine curing agent, and 100 g of flaky silver powder were added thereto, and the mixture was sufficiently stirred until a uniform composition was obtained. Once a homogeneous mixture was obtained, the mixture was dispersed with a 3-roll mill to a particle size of about 30 μm or less.
얻어진 조성물을 사용하여 상기 실시예 1과 동일한 방법으로 시험시편을 제작하고 평가하여, 그 결과를 표 1에 나타내었다.Test specimens were prepared and evaluated in the same manner as in Example 1 using the obtained composition, and the results are shown in Table 1.
<비교예 1>Comparative Example 1
PL2211(일본 GUNNEI CHEM. MFG. 레졸형 페놀수지, 분자량이 500이하임) 25g과 비스페놀 A형 에폭시 수지 YD-011(국도화학제, EEQ 450-500) 25g을 일반 믹서기에서 혼합한 후, 부틸셀로솔브아세테이트 용액 30g을 넣어 잘 혼합하였다. 그 다음, 아민계 경화제인 디시안아미드 5g과 인편상 은분 100g을 넣고 균일 조성물이 될 때까지 충분히 교반하였다. 균일한 혼합물이 얻어지면 3-롤밀로 약 30㎛이하의 입도가 되도록 분산시켰다.Butyl cell after mixing 25 g PL2211 (Japan GUNNEI CHEM.MFG.Resol type phenolic resin, molecular weight less than 500) and 25 g of bisphenol A type epoxy resin YD-011 (manufactured by Kukdo Chemical, EEQ 450-500) in a general mixer 30 g of Rosolve acetate solution was added and mixed well. Then, 5 g of dicyanamide, which is an amine curing agent, and 100 g of flaky silver powder were added thereto, and the mixture was sufficiently stirred until a uniform composition was obtained. Once a homogeneous mixture was obtained, the mixture was dispersed with a 3-roll mill to a particle size of about 30 μm or less.
얻어진 조성물을 사용하여 상기 실시예 1과 동일한 방법으로 시험시편을 제작하고 평가하여, 그 결과를 표 1에 나타내었다.Test specimens were prepared and evaluated in the same manner as in Example 1 using the obtained composition, and the results are shown in Table 1.
<비교예 2>Comparative Example 2
PL2211(일본 GUNNEI CHEM. MFG. 레졸형 페놀수지) 30g과 비스페놀 A형 에폭시 수지 YD-017(국도화학제, EEQ 1750-2100) 20g을 일반 믹서기에서 혼합한 후, 부틸셀로솔브아세테이트 용액 30g을 넣어 잘 혼합하였다. 그 다음, 아민계 경화제인 디시안아미드 5g과 인편상 은분 100g을 넣고 균일 조성물이 될 때까지 충분히 교반하였다. 균일한 혼합물이 얻어지면 3-롤밀로 약 30㎛이하의 입도가 되도록 분산시켰다. 얻어진 조성물을 사용하여 상기 실시예 1과 동일한 방법으로 시험시편을 제작하고 평가하여, 그 결과를 표 1에 나타내었다.30 g of PL2211 (Japan GUNNEI CHEM.MFG.Resol type phenolic resin) and 20 g of bisphenol A type epoxy resin YD-017 (made by Kukdo Chemical, EEQ 1750-2100) were mixed in a general mixer, and then 30 g of butyl cellosolve acetate solution was added. Put and mix well. Then, 5 g of dicyanamide, which is an amine curing agent, and 100 g of flaky silver powder were added thereto, and the mixture was sufficiently stirred until a uniform composition was obtained. Once a homogeneous mixture was obtained, the mixture was dispersed with a 3-roll mill to a particle size of about 30 μm or less. Test specimens were prepared and evaluated in the same manner as in Example 1 using the obtained composition, and the results are shown in Table 1.
이상에서 설명한 바와 같이, 본 발명의 도전성 은 페이스트 조성물은 도전성 및 유연성이 우수하며, 장시간의 온도 사이클 시험과 같은 각종 신뢰성 시험 전후의 도전성 변화가 적어 높은 신뢰성을 유지할 수 있으며, 유동특성이 우수하여 인쇄성이 뛰어나며, 은 쓰루홀 기판용으로 매우 유용하다.As described above, the conductive silver paste composition of the present invention is excellent in conductivity and flexibility, and can maintain high reliability due to few changes in conductivity before and after various reliability tests such as long-term temperature cycle tests, and excellent flow characteristics for printing. It is excellent in its properties and is very useful for through-hole substrates.
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