KR20180090787A - Resin, slurry, laminate using them, and manufacturing method thereof - Google Patents
Resin, slurry, laminate using them, and manufacturing method thereof Download PDFInfo
- Publication number
- KR20180090787A KR20180090787A KR1020187013135A KR20187013135A KR20180090787A KR 20180090787 A KR20180090787 A KR 20180090787A KR 1020187013135 A KR1020187013135 A KR 1020187013135A KR 20187013135 A KR20187013135 A KR 20187013135A KR 20180090787 A KR20180090787 A KR 20180090787A
- Authority
- KR
- South Korea
- Prior art keywords
- resin
- general formula
- group
- carbon atoms
- organic group
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 116
- 239000011347 resin Substances 0.000 title claims abstract description 116
- 239000002002 slurry Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- -1 silane compound Chemical class 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 125000000962 organic group Chemical group 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 239000011135 tin Substances 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 239000011883 electrode binding agent Substances 0.000 abstract 1
- 238000013035 low temperature curing Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 43
- 238000010438 heat treatment Methods 0.000 description 36
- 239000000203 mixture Substances 0.000 description 27
- 239000011342 resin composition Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000004642 Polyimide Substances 0.000 description 15
- 229920001721 polyimide Polymers 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 238000011161 development Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 125000004427 diamine group Chemical group 0.000 description 8
- 125000003709 fluoroalkyl group Chemical group 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004962 Polyamide-imide Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013256 coordination polymer Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229940116333 ethyl lactate Drugs 0.000 description 6
- 229960004592 isopropanol Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920002312 polyamide-imide Polymers 0.000 description 6
- 150000003628 tricarboxylic acids Chemical class 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- 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 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
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- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 239000011149 active material Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
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- 229910052738 indium Inorganic materials 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
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- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
본 발명은, 저온 경화 가능하면서 고강도, 고탄성, 고접착, 저선팽창이며, 리튬 이온 전지, 캐패시터 전극용 결합제에 있어서 양호한 충방전 시의 용량 유지율을 얻는 것이 가능하고, 또한 디바이스 기판의 휨이 적은 반도체 패키지, 디스플레이, 다층 배선 기판을 제작하는 것이 가능한 수지를 제공하는 것을 목적으로 한다. 본 발명은, 청구항 1에 기재된 바와 같이, 일반식 (1)로 표시되는 구조 단위 및/또는 일반식 (2)로 표시되는 구조 단위를 갖는 수지이며, 수지 중에 포함되는 R1 및 R4는, 각각 독립적으로, 적어도 일부에 일반식 (3)으로 표시되는 구조 및 일반식 (4)로 표시되는 구조를 포함하는 수지를 제공한다.Disclosure of the Invention The present invention is to provide a lithium ion battery and a capacitor electrode binder capable of achieving good capacity retention at the time of charge and discharge and capable of achieving low temperature curing and high strength, high elasticity, high adhesion and low linear expansion, It is an object of the present invention to provide a resin capable of producing a package, a display, and a multilayer wiring board. The present invention is a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2) as described in claim 1, wherein R 1 and R 4 , Independently of each other, a resin comprising at least a part of a structure represented by the general formula (3) and a structure represented by the general formula (4).
Description
리튬 이온 이차 전지, 캐패시터 전극용 결합제나 반도체 패키지, 다층 배선 기판, 디스플레이용 절연막으로서 적합하게 사용되는 수지, 슬러리 및 도전성 기재, 도전성 배선 부착 기재와 그들의 적층체와 그의 제조 방법에 관한 것이다.To a resin, a slurry and an electroconductive substrate suitably used as a lithium ion secondary battery, a binder for a capacitor electrode, a semiconductor package, a multilayer interconnection substrate, and an insulating film for a display, a conductive wiring-attached substrate, a laminate thereof and a method of manufacturing the same.
근년, 노트북형 퍼스널 컴퓨터나 소형 휴대 단말기의 폭발적인 보급에 수반하여, 충전 가능한 소형, 경량, 고용량, 고에너지 밀도, 고신뢰성을 갖는 이차 전지에 대한 요구가 강해지고 있다.2. Description of the Related Art In recent years, with the explosion of notebook-type personal computers and small-sized portable terminals, there has been a strong demand for a rechargeable battery having a small size, light weight, high capacity, high energy density and high reliability.
또한 자동차 업계에서는, 전기 자동차(EV)나 하이브리드 전기 자동차(HEV)의 도입에 의한 이산화탄소 배출량의 저감에 기대를 모으고 있으며, 이들 실용화의 키를 쥔 모터 구동용 이차 전지의 개발도 활발히 행해지고 있다.In the automobile industry, development of electric vehicles (EV) and hybrid electric vehicles (HEV) is expected to reduce carbon dioxide emissions, and motor-driven rechargeable batteries having the key to practical use are being actively developed.
특히 전지 중에서 가장 높은 이론 에너지를 갖는다는 리튬 이온 이차 전지가 주목을 모으고 있으며, 현재 급속하게 개발이 진행되고 있다. 현재 널리 사용되고 있는 리튬 이온 전지는, 코발트산리튬 등, 리튬을 포함하는 복합 산화물 등의 정극 활물질과 폴리불화비닐리덴(PVDF) 등의 결합제를 포함하는 페이스트를 알루미늄박 위에 도포하여 형성되는 정극과, 탄소계의 활물질 등, 리튬 이온 흡장 방출 가능한 부극 활물질과 PVDF나 스티렌·부타디엔·고무(SBR) 등의 결합제를 포함하는 페이스트를 구리박 위에 도포하여 형성되는 부극이, 세퍼레이터, 전해질층을 통하여 접속되고, 밀봉된 구성을 갖고 있다.Particularly, lithium ion secondary batteries having the highest theoretical energy among the batteries are attracting attention, and development is progressing rapidly. A widely used lithium ion battery includes a positive electrode formed by applying a paste containing a positive electrode active material such as lithium cobalt oxide and a composite oxide containing lithium and a binder such as polyvinylidene fluoride (PVDF) on an aluminum foil, A negative electrode formed by applying a paste containing a negative electrode active material capable of lithium ion intercalation and deintercalation and a binder such as PVDF or styrene-butadiene rubber (SBR) onto a copper foil such as a carbon-based active material is connected via a separator and an electrolyte layer , And a sealed configuration.
리튬 이온 전지의 용량을 더욱 크게 하기 위하여, 부극 활물질로서 규소, 게르마늄 또는 주석을 사용하는 것이 검토되고 있다(예를 들어, 특허문헌 1 참조). 이와 같이 규소, 게르마늄, 주석 등을 사용한 부극 활물질은, 리튬 이온을 대량으로 수취할 수 있기 때문에, 충분히 충전이 행하여졌을 때와 충분히 방전이 행하여졌을 때의 부피 변화가 커서, 종래의 결합제로는 활물질의 부피 변화를 추종할 수 없기 때문에, 충방전 사이클에서의 용량 유지율이 저하된다. 이 때문에 부피 팽창이 큰 부극용의 결합제의 검토가 이루어지고 있다(예를 들어 특허문헌 2, 3, 4 참조).In order to further increase the capacity of the lithium ion battery, it has been studied to use silicon, germanium or tin as the negative electrode active material (see, for example, Patent Document 1). As described above, the negative electrode active material using silicon, germanium, tin, or the like can receive a large amount of lithium ions. Therefore, when the battery is adequately charged and discharged sufficiently, the volume change is large. The capacity retention rate in the charge / discharge cycle is lowered. For this reason, studies have been made on a binder for a negative electrode having a large volume expansion (see, for example, Patent Documents 2, 3 and 4).
또한 노트북형 퍼스널 컴퓨터나 소형 휴대 단말기의 고속화, 소형화는 반도체, 디스플레이, 다층 배선 기판 등의 부품의 소형화, 박화를 진행하고, 그것에 수반하여 디바이스 기판의 휨에 기인하는 공정 수율의 악화나 디바이스의 신뢰성에 대한 악영향이 염려되고 있다. 이로 인해, 수지에도 기판의 휨을 작게 하는 특성의 부여가 요구되고 있다.In addition, high-speed and miniaturization of notebook-type personal computers and small-sized portable terminals have led to miniaturization and thinning of parts such as semiconductors, displays, and multilayer wiring boards, and consequently, deterioration of process yields due to warping of device substrates, There is a concern about the adverse effect on the environment. For this reason, it is required to give the resin a characteristic of reducing warping of the substrate.
디바이스 기판의 휨을 작게 하는 방법으로서는, 기판 위에 제막된 수지와 기판 그 자체의 열선팽창 계수의 차를 작게 하여, 열 팽창차에 의해 발생하는 응력을 작게 하는 것을 들 수 있다. 일반적인 수지의 열선팽창 계수는 기판의 열선팽창 계수보다도 10ppm 이상 크기 때문에, 상기한 응력 저감을 위해서는 수지의 열선팽창 계수를 작게 하는 것이 효과적이다. 본 과제를 달성하기 위하여 주쇄에 강직한 구조를 포함한 열선팽창 계수가 작은 폴리이미드계 수지(예를 들어, 특허문헌 5 내지 9 참조) 등이 보고되어 있다.As a method for reducing the warpage of the device substrate, there is a method in which the difference in thermal expansion coefficient between the resin deposited on the substrate and the substrate itself is reduced, and the stress caused by the thermal expansion difference is reduced. Since the thermal expansion coefficient of a general resin is 10 ppm or more larger than the thermal expansion coefficient of the substrate, it is effective to reduce the thermal expansion coefficient of the resin in order to reduce the stress described above. Polyimide-based resins (for example, see Patent Documents 5 to 9) having a structure with rigidity in the main chain and having a small thermal expansion coefficient have been reported in order to achieve this task.
그러나, 특허문헌 1에 부피 팽창이 큰 부극에 대한 구체적인 결합제로서 기재되어 있는 카르복시메틸셀룰로오스의 나트륨염으로는, 강도가 아직 부족하고 충방전 사이클에서 충분한 용량 유지율을 얻을 수 없다는 문제가 있었다.However, in Patent Document 1, the sodium salt of carboxymethyl cellulose described as a specific binder for the negative electrode having a large volume expansion has a problem that the strength is still insufficient and a sufficient capacity retention rate can not be obtained in a charge-discharge cycle.
특허문헌 2에 기재된 폴리이미드 결합제로는, 결합제의 강도는 높지만, 폴리이미드 구조로 전환하기 위하여 전극 제작 시에 300℃ 이상의 고온 처리를 행해야 하므로, 전극의 산화 열화 등의 문제가 있었다.As the polyimide bonding agent disclosed in Patent Document 2, although the strength of the bonding agent is high, there is a problem in that the electrode is deteriorated in oxidation because the bonding process needs to be performed at a high temperature of 300 ° C or higher at the time of manufacturing an electrode in order to switch to a polyimide structure.
특허문헌 3 및 4에 기재된 결합제로는, 결합제의 강도는 높게, 처리 온도도 낮게 할 수 있지만, 충방전 시의 부피 변화에 의한 전극의 열화를 억제하여 높은 용량 유지율을 얻기에는, 막 물성이 아직 불충분하다는 문제가 있었다.As the binder described in Patent Documents 3 and 4, the strength of the binder can be made high and the processing temperature can be made low. However, in order to suppress deterioration of the electrode due to volume change during charging and discharging and to obtain a high capacity retention rate, There was a problem that it was insufficient.
또한, 특허문헌 5 내지 9에 기재된 폴리이미드는 폴리이미드 구조로 전환하기 위하여 300℃ 이상의 고온 처리를 행해야 하므로, 디바이스의 산화 열화 등의 문제가 있었다.In addition, the polyimides described in Patent Documents 5 to 9 have to be subjected to a high-temperature treatment at 300 DEG C or more in order to convert to a polyimide structure.
그래서 본 발명은, 저온 처리 가능하며, 또한 처리 후의 막이 고강도, 고탄성, 고접착, 저열선팽창인 수지, 슬러리 및 그들을 도전성 기재, 도전성 배선 부착 기재에 제막된 적층체를 제공하는 것을 과제로 한다.SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a laminate obtained by coating a resin, a slurry and a conductive base material, which have a high strength, a high elasticity, a high adhesion and a low heat linear expansion,
즉 본 발명은, 일반식 (1)로 표시되는 구조 단위 및/또는 하기 일반식 (2)로 표시되는 구조 단위를 갖는 수지이며, 수지 중에 포함되는 R1 및 R4는, 각각 독립적으로, 적어도 일부에 하기 일반식 (3)으로 표시되는 구조 및 하기 일반식 (4)로 표시되는 구조를 포함하는 수지이다.That is, the present invention is a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the following general formula (2), wherein R 1 and R 4 contained in the resin are each independently Is a resin containing in part a structure represented by the following general formula (3) and a structure represented by the following general formula (4).
(일반식 (1) 중 R1은 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R2는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. R3은 수소 원자 또는 탄소수 1 내지 10의 유기기를 나타낸다. m1은 1 또는 2의 정수이다.)(In the general formula (1), R 1 represents a divalent organic group having 2 to 50 carbon atoms, R 2 represents a tricyclic or tetravalent organic group having 2 to 50 carbon atoms, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms M < 1 > is an integer of 1 or 2.)
(일반식 (2) 중 R4는 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R5는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. m2는 0 또는 1의 정수, c1은 0 또는 1의 정수이며, m2=0일 때 c1=1, m2=1일 때 c1=0이다.)(Formula (2): R 4 represents a divalent organic group having 2 to 50. R 5 is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M 2 is an integer, c 1 0 or 1, Is an integer of 0 or 1, c 1 = 1 when m 2 = 0, and c 1 = 0 when m 2 = 1.)
(일반식 (3) 중 R6, R7은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b1 및 b2는 각각 독립적으로 0 내지 3의 정수이다.)(In the general formula (3), R 6 and R 7 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b 1 and b 2 each independently represent an integer of 0 to 3.)
(일반식 (4) 중 R8은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b3은 0 내지 4의 정수이다.)(In the general formula (4), R 8 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b 3 is an integer of 0 to 4)
본 발명의 수지에 의하면, 저온 경화 가능하면서 고강도, 고탄성, 고접착, 저선팽창이며, 리튬 이온 전지, 캐패시터 전극용 결합제에 있어서 양호한 충방전 시의 용량 유지율을 얻는 것이 가능하고, 또한, 디바이스 기판의 휨이 낮은 반도체 패키지, 디스플레이, 다층 배선 기판을 제작하는 것이 가능해진다.According to the resin of the present invention, it is possible to obtain a capacity retention rate at the time of good charging and discharging in a binder for a lithium ion battery and a capacitor electrode, which can be cured at a low temperature and has high strength, high elasticity, high adhesion and low linear expansion, A semiconductor package, a display, and a multilayer wiring board with low warpage can be manufactured.
본 발명의 수지는, 하기 일반식 (1) 및 (2) 중 적어도 하나로부터 선택되는 구조 단위를 갖는 수지이다.The resin of the present invention is a resin having a structural unit selected from at least one of the following general formulas (1) and (2).
(일반식 (1) 중 R1은 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R2는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. R3은 수소 원자 또는 탄소수 1 내지 10의 유기기를 나타낸다. m1은 1 또는 2의 정수이다.)(In the general formula (1), R 1 represents a divalent organic group having 2 to 50 carbon atoms, R 2 represents a tricyclic or tetravalent organic group having 2 to 50 carbon atoms, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms M < 1 > is an integer of 1 or 2.)
(일반식 (2) 중 R4는 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R5는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. m2는 0 또는 1의 정수, c1은 0 또는 1의 정수이며, m2=0일 때 c1=1, m2=1일 때 c1=0이다.)(Formula (2): R 4 represents a divalent organic group having 2 to 50. R 5 is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M 2 is an integer, c 1 0 or 1, Is an integer of 0 or 1, c 1 = 1 when m 2 = 0, and c 1 = 0 when m 2 = 1.)
보다 저온에서 처리 가능하다는 관점에서, 일반식 (2)로 표시되는 구조 단위를 주성분으로 하는 수지인 것이 바람직하고, 용매에 대한 가용성이라는 관점에서 m2는 0인 폴리아미드이미드 구조인 것이 더욱 바람직하다.From the viewpoint of being able to be treated at a lower temperature, it is preferably a resin containing a structural unit represented by the general formula (2) as a main component, more preferably a polyamideimide structure in which m 2 is 0 in view of solubility in a solvent .
여기에서 말하는 주성분이란 전체 수지 중 70중량% 이상, 바람직하게는 80중량% 이상인 것을 가리킨다.As used herein, the main component means at least 70 wt%, preferably at least 80 wt% of the total resin.
일반식 (1) 및 (2) 중 R1, R4는 디아민 잔기를 나타내고, 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R1 및 R4는, 각각 독립적으로, 일반식 (3)으로 표시되는 구조 및 일반식 (4)로 표시되는 구조를 포함한다.In the general formulas (1) and (2), R 1 and R 4 represent a diamine residue and represent a divalent organic group having 2 to 50 carbon atoms. R 1 and R 4 each independently represent a structure represented by formula (3) and a structure represented by formula (4).
일반식 (3) 중 R6, R7은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. 수지의 선팽창 계수를 저감시킬 수 있다는 점에서, 바람직하게는 불소 원자, 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기, 보다 바람직하게는 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기이다.In the general formula (3), R 6 and R 7 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced.
b1 및 b2는 각각 독립적으로 0 내지 3의 정수이다. 용매에 대한 가용성과 저선팽창성의 양립이라는 점에서, 바람직하게는 1 또는 2이다. 또한, 저선팽창성의 관점에서, R6 및 R7은 중합체 주쇄에 대하여 오르토 위치에 결합되어 있는 것이 바람직하다.b 1 and b 2 are each independently an integer of 0 to 3; And is preferably 1 or 2 in terms of compatibility with a solvent and low linear expansion property. From the viewpoint of low linear expansion property, it is preferable that R 6 and R 7 are bonded to the ortho position with respect to the polymer main chain.
일반식 (3) 중 저선팽창 특성의 관점에서, 바람직하게는 벤젠환이 파라 결합으로 연결되어 있는 것이다. 구체적으로는 하기에 표시하는 구조의 것을 들 수 있지만, 이들에 한정되지 않는다.From the viewpoint of the low linear expansion characteristic of the general formula (3), the benzene ring is preferably connected to a para bond. Specific examples include those having the structures shown below, but are not limited thereto.
용매에 대한 가용성과 저선팽창성의 양립의 관점에서, R1 및 R4는, 각각 독립적으로, 그의 50몰% 이상이 일반식 (3)으로 표시되는 구조인 것이 바람직하고, 70몰% 이상이 갖는 것이 보다 바람직하다.From the viewpoint of compatibility between the solubility in the solvent and the low linear expansion property, R 1 and R 4 each independently preferably have a structure represented by the formula (3) in which 50 mol% or more thereof is contained and 70 mol% or more Is more preferable.
일반식 (4) 중 R8은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. 수지의 선팽창 계수를 저감시킬 수 있다는 점에서, 바람직하게는 불소 원자, 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기, 보다 바람직하게는 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기이다. b3은 0 내지 4의 정수이다. 용매에 대한 가용성과 저선팽창성의 양립이라는 점에서 바람직하게는 1 또는 2이다. 또한, 저선팽창성의 관점에서, R8은 중합체 주쇄에 대하여 오르토 위치에 결합되어 있는 것이 가장 바람직하다.In the general formula (4), R 8 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. b 3 is an integer of 0 to 4; But is preferably 1 or 2 in view of compatibility between solubility in solvents and low linear expansion properties. From the viewpoint of low linear expansion property, it is most preferable that R 8 is bonded to the ortho position with respect to the polymer main chain.
일반식 (4) 중 용매에 대한 가용성과 저선팽창성의 양립의 관점에서, 벤젠환이 메타 결합으로 연결되어 있는 것이 바람직하다. 구체적으로는 하기에 표시하는 구조의 것을 들 수 있지만, 이들에 한정되지 않는다.From the viewpoint of compatibility between the solubility in solvent and low linear expansion property in the general formula (4), it is preferable that the benzene ring is connected by a meta bond. Specific examples include those having the structures shown below, but are not limited thereto.
용매에 대한 가용성과 저선팽창성의 양립의 관점에서, R1 및 R4는, 각각 독립적으로, 그의 10 내지 40몰%가 일반식 (4)로 표시되는 구조인 것이 바람직하고, 보다 바람직하게는 25 내지 35몰%이다.From the viewpoint of both compatibility with the solvent and low linear expansion property, it is preferable that R 1 and R 4 each independently represent a structure represented by the general formula (4) in an amount of 10 to 40 mol%, more preferably 25 To 35 mol%.
디아민 잔기는, 일반식 (3), (4)로 표시되는 구조 이외의 디아민 잔기를 포함하고 있어도 된다. 그러한 디아민 잔기를 부여하는 아민 성분으로서는, 3,5-디아미노벤조산, 3-카르복시-4,4'-디아미노디페닐에테르 등의 카르복실기 함유 디아민, 3-술폰산-4,4'-디아미노디페닐에테르 등의 술폰산 함유 디아민, 디티오히드록시페닐렌디아민, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐메탄, 3,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐술폰, 3,4'-디아미노디페닐술피드, 4,4'-디아미노디페닐술피드, 1,4-비스(4-아미노페녹시)벤젠, 1,5-나프탈렌디아민, 2,6-나프탈렌디아민, 비스(4-아미노페녹시페닐)술폰, 비스(3-아미노페녹시페닐)술폰, 비스(4-아미노페녹시)비페닐, 비스{4-(4-아미노페녹시)페닐}에테르, 1,4-비스(4-아미노페녹시)벤젠 혹은 이들의 방향족환의 수소 원자의 일부를 알킬기나 할로겐 원자로 치환한 화합물이나, 시클로헥실디아민, 메틸렌비스시클로헥실아민 등의 지방족 디아민 등을 들 수 있지만 이들에 한정되지 않는다.The diamine residue may contain a diamine residue other than the structures represented by the general formulas (3) and (4). Examples of the amine component imparting such a diamine residue include a carboxyl group-containing diamine such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether, a 3-sulfonic acid- Containing diamine such as phenyl ether, diethoxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-dia (4-aminophenoxy) benzene, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis (4-aminophenoxyphenyl) sulfone, bis Bis (4-aminophenoxy) benzene or an aromatic ring thereof, or an aromatic ring thereof, A part of the hydrogen atoms may be substituted with an alkyl group or a halogen atom And the like, or a compound, cyclohexyl diamine, an aliphatic diamine such as methylene-bis-cyclohexyl amine, but not limited to these.
이들 디아민 잔기를 부여하는 원료로서는, 디아민 이외에도, 디아민 잔기의 구조에 아미노기 대신 이소시아네이트기가 결합한 디이소시아네이트 화합물이나, 디아민의 아미노기의 2개의 수소 원자가 트리메틸실릴기로 치환된 테트라트리메틸실릴화디아민을 사용할 수도 있다.As a raw material for imparting these diamine residues, a diisocyanate compound having an isocyanate group bonded to the structure of the diamine residue instead of the amino group or a tetra-trimethylsilylated diamine in which two hydrogen atoms of the diamine amino group are substituted with trimethylsilyl groups may be used.
일반식 (2)로 표시되는 구조 단위를 주성분으로 하는 수지인 경우, 부생되는 수분이 없다는 점에서 디이소시아네이트 화합물이 바람직하게 사용된다.In the case of a resin containing a structural unit represented by the general formula (2) as a main component, a diisocyanate compound is preferably used because it is free from water as a by-product.
일반식 (1) 및 (2) 중 R2 및 R5는 트리- 또는 테트라-카르복실산 잔기(이하, 「산 잔기」라고 한다)를 나타낸다.In the general formulas (1) and (2), R 2 and R 5 represent a tri- or tetra-carboxylic acid residue (hereinafter referred to as "acid residue").
산 잔기를 부여하는 바람직한 트리카르복실산의 예로서, 트리멜리트산, 트리메스산, 디페닐에테르트리카르복실산, 비페닐트리카르복실산 등을 들 수 있다.Examples of preferred tricarboxylic acids to which acid residues are imparted include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid.
산 잔기를 부여하는 바람직한 테트라카르복실산의 예로서, 피로멜리트산, 3,3',4,4'-비페닐테트라카르복실산, 2,3,3',4'-비페닐테트라카르복실산, 2,2',3,3'-비페닐테트라카르복실산, 3,3',4,4'-벤조페논테트라카르복실산, 2,2',3,3'-벤조페논테트라카르복실산, 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판, 2,2-비스(2,3-디카르복시페닐)헥사플루오로프로판, 1,1-비스(3,4-디카르복시페닐)에탄, 1,1-비스(2,3-디카르복시페닐)에탄, 비스(3,4-디카르복시페닐)메탄, 비스(2,3-디카르복시페닐)메탄, 비스(3,4-디카르복시페닐)술폰, 비스(3,4-디카르복시페닐)에테르, 1,2,5,6-나프탈렌테트라카르복실산, 2,3,6,7-나프탈렌테트라카르복실산, 2,3,5,6-피리딘테트라카르복실산, 3,4,9,10-페릴렌테트라카르복실산 등의 방향족 테트라카르복실산이나, 시클로부탄테트라카르복실산, 1,2,3,4-시클로펜탄테트라카르복실산, 시클로헥산테트라카르복실산, 비시클로[2.2.1.]헵탄테트라카르복실산, 비시클로[3.3.1.]테트라카르복실산, 비시클로[3.1.1.]헵토-2-엔테트라카르복실산, 비시클로[2.2.2.]옥탄테트라카르복실산, 아다만탄테트라카르복실산 등의 지방족 테트라카르복실산 등을 들 수 있다. 이들 산은, 단독 또는 2종 이상을 조합하여 사용할 수 있다.Examples of preferred tetracarboxylic acids for imparting acid residues include pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid Acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracar (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis Bis (2,3-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis , 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2 , 3,5,6-pyridine tetracarboxylic acid, and 3,4,9,10-perylene tetracarboxylic acid; aromatic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,3,4 -city Cyclohexanetetracarboxylic acid, bicyclo [2.2.1.] Heptane tetracarboxylic acid, bicyclo [3.3.1.] Tetracarboxylic acid, bicyclo [3.1.1.] Hepto 2-ene tricarboxylic acid, bicyclo [2.2.2.] Octane tetracarboxylic acid, and adamantanetetracarboxylic acid. These acids may be used alone or in combination of two or more.
수지의 저선팽창성의 관점에서, R2 및 R5는, 각각 독립적으로, 그의 65몰% 이상이 일반식 (5), (6) 중 적어도 하나로부터 선택되는 구조인 것이 바람직하다.From the viewpoint of the low linear expansion property of the resin, it is preferable that R 2 and R 5 each independently be a structure in which at least 65 mol% thereof is selected from at least one of the general formulas (5) and (6).
일반식 (5), (6) 중 R9, R10은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. 수지의 선팽창 계수를 저감시킬 수 있다는 점에서, 바람직하게는 불소 원자, 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기, 보다 바람직하게는 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기이다. b4, b5는 0 내지 4의 정수이다. 저선팽창성이라는 점에서 바람직하게는 0이다. 구체적으로는 하기에 표시하는 구조의 것을 들 수 있지만, 이들에 한정되지 않는다.In the general formulas (5) and (6), R 9 and R 10 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. and b 4 and b 5 are an integer of 0 to 4. And is preferably 0 in terms of low linear expansion. Specific examples include those having the structures shown below, but are not limited thereto.
또한 본 발명의 수지는, 추가로, 고강도, 고탄성으로 하기 위하여, 하기 일반식 (7)로 표시되는 구조 단위를 5 내지 30몰% 포함하는 것이 바람직하다.The resin of the present invention preferably further contains 5 to 30 mol% of the structural unit represented by the following general formula (7) in order to obtain high strength and high elasticity.
일반식 (7) 중 R11은 디아민 잔기를 나타내고, 탄소수 2 내지 50의 2가의 유기기를 나타낸다. 디아민 잔기를 부여하는 아민 성분으로서는, 3,5-디아미노벤조산, 3-카르복시-4,4'-디아미노디페닐에테르 등의 카르복실기 함유 디아민, 3-술폰산-4,4'-디아미노디페닐에테르 등의 술폰산 함유 디아민, 디티오히드록시페닐렌디아민, 3,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐메탄, 3,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐술폰, 3,4'-디아미노디페닐술피드, 4,4'-디아미노디페닐술피드, 1,4-비스(4-아미노페녹시)벤젠, m-페닐렌디아민, p-페닐렌디아민, 1,5-나프탈렌디아민, 2,6-나프탈렌디아민, 비스(4-아미노페녹시페닐)술폰, 비스(3-아미노페녹시페닐)술폰, 비스(4-아미노페녹시)비페닐, 비스{4-(4-아미노페녹시)페닐}에테르, 1,4-비스(4-아미노페녹시)벤젠, 2,2'-디메틸-4,4'-디아미노비페닐, 2,2'-디에틸-4,4'-디아미노비페닐, 3,3'-디메틸-4,4'-디아미노비페닐, 3,3'-디에틸-4,4'-디아미노비페닐, 2,2',3,3'-테트라메틸-4,4'-디아미노비페닐, 3,3',4,4'-테트라메틸-4,4'-디아미노비페닐, 2,2'-디(트리플루오로메틸)-4,4'-디아미노비페닐, 혹은 이들 방향족환의 수소 원자의 일부를 알킬기나 할로겐 원자로 치환한 화합물이나, 일반식 (3), (4)로 표시되는 구조, 시클로헥실디아민, 메틸렌비스시클로헥실아민 등의 지방족 디아민 등을 들 수 있지만 이들에 한정되지 않는다.In the general formula (7), R 11 represents a diamine residue and represents a divalent organic group having 2 to 50 carbon atoms. Examples of the amine component that imparts the diamine residue include carboxyl group-containing diamines such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether, and 3-sulfonic acid-4,4'-diaminodiphenyl Dihydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diamino (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) phenyl} sulfone, bis (3-aminophenoxy) sulfone, bis -Aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'- Tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4 , 4'-diaminobiphenyl, or compounds obtained by substituting a part of the hydrogen atoms of these aromatic rings with an alkyl group or a halogen atom, a structure represented by the general formula (3) or (4), a cyclohexyldiamine, a methylenebiscyclohexylamine , And the like, but are not limited thereto.
이들 디아민은, 그대로, 혹은 대응하는 디이소시아네이트 화합물이나 트리메틸실릴화디아민으로서 사용할 수도 있다. 부생되는 수분이 없다는 점에서 디이소시아네이트 화합물이 바람직하게 사용된다.These diamines may be used as such or as a corresponding diisocyanate compound or trimethylsilylated diamine. A diisocyanate compound is preferably used in that no water is produced as a by-product.
R12는 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. 수지의 선팽창 계수를 저감시킬 수 있다는 점에서, 바람직하게는 불소 원자, 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기, 보다 바람직하게는 탄소수 1 내지 3의 알킬기 또는 플루오로알킬기이다. b6은 0 내지 4의 정수이다. 저선팽창성이라는 점에서 바람직하게는 0이다.Each R 12 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. and b 6 is an integer of 0 to 4. And is preferably 0 in terms of low linear expansion.
일반식 (7) 중 저선팽창 특성의 관점에서, 바람직하게는 벤젠환이 파라 결합으로 연결되어 있는 것이다.From the viewpoint of the low linear expansion characteristic of the general formula (7), the benzene ring is preferably connected to a para bond.
일반식 (1), (2), (7)에 있어서, 가열 처리 후의 피막의 실리콘계 기판, 유리 기판과의 접착성을 향상시키기 위하여 또는 세정 등에 사용되는 산소 플라스마, UV 오존 처리에 대한 내성을 높이기 위하여, 내열성을 저하시키지 않는 범위에서, R1, R4, R11, R2, R5에 실록산 구조를 공중합해도 된다. 구체적인 R1, R4, R11의 예로서는 비스(3-아미노프로필)테트라메틸디실록산, 비스(p-아미노-페닐)옥타메틸헵타실록산 등의 잔기 등을 들 수 있다. 이들은 R1, R4, R11 전체의 1 내지 10몰% 공중합되어 있는 것이 바람직하다. 구체적인 R2, R5의 예로서는 디메틸실란디프탈산 이무수물, 1,3-비스(프탈산)테트라메틸디실록산 이무수물, 1-(p-카르복시페닐) 3-프탈산-1,1,3,3-테트라메틸디실록산 등의 잔기 등을 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 사용되고, R2, R5 전체의 1 내지 10몰% 공중합되어 있는 것이 바람직하다.In the general formulas (1), (2) and (7), it is preferable to increase the resistance to oxygen plasma and UV ozone treatment used for improving the adhesiveness of the coating film after heat treatment with the silicone- , A siloxane structure may be copolymerized with R 1 , R 4 , R 11 , R 2 and R 5 within a range not lowering the heat resistance. Specific examples of R 1 , R 4 and R 11 include residues such as bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylheptasiloxane. They are preferably copolymerized with 1 to 10 mol% of all of R 1 , R 4 and R 11 . Specific examples of R 2 and R 5 include dimethylsilyldiphthalic dianhydride, 1,3-bis (phthalic acid) tetramethyldisiloxane dianhydride, 1- (p-carboxyphenyl) 3-phthalic acid- And residues such as tetramethyldisiloxane. These may be used singly or in combination of two or more, preferably 1 to 10 mol% of all R 2 and R 5 .
일반식 (1), (2), (7)에 있어서, 가열 처리 후의 피막의 금속 기판과의 접착성을 향상시키기 위하여, 내열성을 저하시키지 않는 범위에서, R1, R4, R11에 폴리알킬렌옥사이드기를 갖는 지방족 구조를 공중합해도 된다. 구체적인 구조로서, "제파민"(등록 상표) KH-511, 제파민 ED-600, 제파민 ED-900, 제파민 ED-2003, 제파민 EDR-148, 제파민 EDR-176, 제파민 D-200, 제파민 D-400, 제파민 D-2000, 제파민 D-4000(이상 상품명. HUNTSMAN(주)제) 등의 잔기를 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 사용되고, R1, R4, R11 전체의 1 내지 30몰% 공중합되어 있는 것이 바람직하다.R 1 , R 4 , and R 11 are bonded to the poly (alkylene oxide) of the poly (alkylene oxide) of the general formula (1), (2), and (7) An aliphatic structure having an alkylene oxide group may be copolymerized. As a specific structure, there may be mentioned "JEMPAMIN" (registered trademark) KH-511, JEMFAMINE ED-600, JEMPAMINE ED-900, JEMPAMINE ED- 200, Jeffamine D-400, Jeffamine D-2000 and Jeffamine D-4000 (trade names, manufactured by HUNTSMAN). These may be used singly or in combination of two or more, preferably 1 to 30 mol% of all of R 1 , R 4 and R 11 .
이들 수지는 하기에 예시한 방법으로 합성되지만, 이들에 한정되지 않는다. 즉, 일반식 (1)로 표시되는 폴리아미드산의 경우, 디아민을 N-메틸피롤리돈(NMP), N,N-디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAC), 감마부티로락톤(GBL), 디메틸술폭시드(DMSO) 등의 용매에 용해하고, 테트라카르복실산 이무수물을 첨가하여 반응시키는 방법이 일반적이다. 반응 온도는 -20℃ 내지 100℃가 일반적이고, 0℃ 내지 50℃가 바람직하다. 반응 시간은 1분간 내지 100시간이 일반적이고, 2시간 내지 24시간이 바람직하다. 반응 중에는 질소를 흐르게 하거나 하여 수분이 계내에 들어가지 않도록 하는 것이 바람직하다.These resins are synthesized by the methods exemplified below, but are not limited thereto. Namely, in the case of the polyamic acid represented by the general formula (1), the diamine is reacted with N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC) Is dissolved in a solvent such as gamma-butyrolactone (GBL) or dimethylsulfoxide (DMSO), and then a tetracarboxylic acid dianhydride is added to react. The reaction temperature is generally -20 ° C to 100 ° C, and preferably 0 ° C to 50 ° C. The reaction time is generally 1 minute to 100 hours, preferably 2 hours to 24 hours. During the reaction, it is preferable to flow nitrogen to prevent moisture from entering the system.
일반식 (1)로 표시되는 폴리아미드산에스테르의 경우, 테트라카르복실산 이무수물을 에탄올, 프로판올, 부탄올 등의 알코올과 피리딘이나 트리에틸아민 등의 염기 촉매와 혼합하고, 실온 내지 100℃에서 수분간 내지 10시간 정도 반응시켜, 디카르복실산디에스테르 화합물을 얻는다. 또한, 테트라카르복실산 이무수물을 직접 알코올에 분산시켜도 되고, 테트라카르복실산 이무수물을 NMP, DMAC, DMF, DMSO, GBL 등의 용매에 용해시켜, 알코올과 염기 촉매를 작용시켜도 된다. 얻어진 디카르복실산디에스테르를, 티오닐클로라이드 중에서 가열 처리하거나, 옥잘로디클로라이드를 작용시키거나 하여 디카르복실산클로라이드디에스테르로 한다. 얻어진 디카르복실산클로라이드디에스테르를 증류 등의 방법으로 회수하고, 피리딘이나 트리에틸아민의 존재 하에서, 디아민을 NMP, DMAC, DMF, DMSO, GBL 등의 용매에 용해한 용액에 적하한다. 적하는 -20℃ 내지 30℃에서 실시하는 것이 바람직하다. 적하 종료 후, -20℃ 내지 50℃에서 1시간 내지 100시간 반응시켜 폴리아미드산에스테르를 얻는다. 또한, 디카르복실산디클로라이드디에스테르를 사용하면 부생성물로서 염산염이 생기기 때문에, 디카르복실산디에스테르를, 티오닐클로라이드 중에서 가열 처리하거나, 옥잘로디클로라이드를 작용시키거나 하는 대신, 디시클로헥실카르보디이미드 등의 펩티드의 축합 시약에 의해 디아민과 반응시키는 것이 바람직하다. 또한, 앞서 설명한 폴리아미드산에 디메틸포름아미드디알킬아세탈 등의 아세탈 화합물을 반응시킴으로써도 폴리아미드산에스테르를 얻을 수 있다. 아세탈 화합물의 첨가량에 의해 에스테르화율을 조정할 수 있다.In the case of the polyamic acid ester represented by the general formula (1), the tetracarboxylic acid dianhydride is mixed with an alcohol such as ethanol, propanol, and butanol and a base catalyst such as pyridine or triethylamine, For about 10 minutes to 10 hours to obtain a dicarboxylic acid diester compound. Alternatively, the tetracarboxylic dianhydride may be directly dispersed in the alcohol, or the tetracarboxylic dianhydride may be dissolved in a solvent such as NMP, DMAC, DMF, DMSO, GBL, or the like to effect the action of an alcohol and a base catalyst. The resulting dicarboxylic acid diester is subjected to a heat treatment in thionyl chloride or to act on oxalodichloride to obtain a dicarboxylic acid chloride diester. The obtained dicarboxylic acid chloride diester is recovered by a method such as distillation and is dropwise added to a solution in which diamine is dissolved in a solvent such as NMP, DMAC, DMF, DMSO or GBL in the presence of pyridine or triethylamine. Is preferably carried out at -20 캜 to 30 캜. After completion of the dropwise addition, the reaction is carried out at -20 캜 to 50 캜 for 1 hour to 100 hours to obtain a polyamic acid ester. In addition, when a dicarboxylic acid dichloride diester is used, a hydrochloride salt is produced as a by-product. Therefore, instead of heating the dicarboxylic acid diester in thionyl chloride or using oxalodichloride, dicyclohexylcarbodi It is preferable to react with a diamine by a condensing reagent for a peptide such as a peptide or a peptide. The polyamic acid ester can also be obtained by reacting the above-described polyamic acid with an acetal compound such as dimethylformamide dialkyl acetal. The esterification rate can be adjusted by the amount of the acetal compound added.
일반식 (2)로 표시되는 폴리이미드의 경우, 상기 폴리이미드 전구체를 가열 처리나 화학 처리에 의해 이미드 폐환함으로써 얻을 수 있다. 화학 처리로서는, 무수 아세트산과 피리딘에 의한 처리, 트리에틸아민, 도데실운데센 등의 염기 처리, 무수 아세트산, 무수 숙신산 등의 산 무수물 처리 등을 들 수 있다.In the case of the polyimide represented by the general formula (2), the polyimide precursor can be obtained by subjecting the polyimide precursor to heat treatment or chemically treating the imide ring. Examples of the chemical treatment include treatment with acetic anhydride and pyridine, base treatment such as triethylamine and dodecyl undecene, and acid anhydride treatment with acetic anhydride and succinic anhydride.
일반식 (2)로 표시되는 폴리아미드이미드의 경우, 디아민을 NMP, DMF, DMAC, GBL, DMSO 등의 용매에 용해하고, 트리카르복실산을 첨가하여 반응시키는 방법이 일반적이다. 반응 온도는 -20℃ 내지 100℃가 일반적이고, 0℃ 내지 50℃가 바람직하다. 반응 시간은 1분간 내지 100시간이 일반적이므로, 2시간 내지 24시간이 바람직하다. 반응 중에는 질소를 흐르게 하거나 하여 수분이 계내에 들어가지 않도록 하는 것이 바람직하다. 일반적인 반응으로서는, 디아민 용액에 트리카르복실산클로라이드를 작용시키고, 그 후, 100℃ 내지 300℃의 가열 처리를 1분 내지 24시간 행하여, 폴리아미드이미드를 얻는 방법이 있다. 이 경우, 이미드화를 위하여 무수 아세트산 등의 산 무수물이나 트리에틸아민, 피리딘, 피콜린 등의 염기를 촉매로서 중합체량에 대하여 0.l 내지 10중량% 첨가하여 반응을 촉진할 수도 있다. 또한, 디아민과 무수 트리멜리트산클로라이드를 피리딘, 트리에틸아민 등의 존재 하에서, 폴리아미드산아미드를 중합하고, 이 중합체를 고체로 취출하고, 그 후, 고체를 100 내지 300℃의 온도에서 1분 내지 24시간 가열하여 폴리아미드이미드를 얻을 수도 있다.In the case of the polyamideimide represented by the general formula (2), a method of dissolving the diamine in a solvent such as NMP, DMF, DMAC, GBL or DMSO and adding a tricarboxylic acid is generally used. The reaction temperature is generally -20 ° C to 100 ° C, and preferably 0 ° C to 50 ° C. The reaction time is generally from 1 minute to 100 hours, and therefore, it is preferably from 2 hours to 24 hours. During the reaction, it is preferable to flow nitrogen to prevent moisture from entering the system. As a general reaction, there is a method in which a diamine solution is reacted with tricarboxylic acid chloride, and then heat treatment at 100 ° C to 300 ° C is performed for 1 minute to 24 hours to obtain a polyamideimide. In this case, for the imidization, an acid anhydride such as acetic anhydride or a base such as triethylamine, pyridine, or picoline may be added as a catalyst in an amount of 0.1 to 10 wt% based on the amount of the polymer to accelerate the reaction. The diamine and trimellitic anhydride chloride are polymerized with a polyamide acid amide in the presence of pyridine, triethylamine, etc., and the polymer is taken out as a solid. Thereafter, the solid is heated at a temperature of 100 to 300 DEG C for 1 minute For 24 hours to obtain a polyamideimide.
일반식 (2)로 표시되는 폴리이미드, 폴리아미드이미드의 경우, 디아민 화합물의 아미노기를 이소시아네이트 대신, 테트라카르복실산 이무수물, 트리카르복실산 무수물 등의 2가 이상의 산과, 경우에 따라서는 주석계 촉매나 염기 촉매의 존재 하에, 실온 내지 200℃의 온도 범위에서 1분 내지 24시간 반응시킴으로써 더 얻을 수도 있다. 이 방법은 부생되는 수분이 없다는 점에서 보다 바람직한 방법이라고 할 수 있다.In the case of the polyimide or polyamideimide represented by the general formula (2), the amino group of the diamine compound may be replaced by an acid having a valence of 2 or more such as tetracarboxylic acid dianhydride or tricarboxylic acid anhydride instead of isocyanate, In the presence of a catalyst or a base catalyst at a temperature ranging from room temperature to 200 ° C for 1 minute to 24 hours. This method is more preferable in that there is no by-produced water.
이들 수지의 중합 반응에 있어서 산 성분의 디아민 혹은 디이소시아네이트에 대한 몰 비율은, 디아민 혹은 디이소시아네이트 100몰%에 대하여 100몰% 이하, 바람직하게는 95몰% 이하, 더욱 바람직하게는 90몰% 이하, 가장 바람직하게는 85몰% 이하이다. 디아민 혹은 디이소시아네이트가 더 많으면 말단 아민, 이소시아네이트기가 수지와 필러, 도전성 기재, 도전성 배선의 접착성을 높인다는 효과가 있다.The molar ratio of the acid component to the diamine or diisocyanate in the polymerization reaction of these resins is 100 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, based on 100 mol% of diamine or diisocyanate , And most preferably 85 mol% or less. When the amount of the diamine or the diisocyanate is larger, there is an effect that the terminal amine and the isocyanate group increase the adhesion between the resin and the filler, the conductive base and the conductive wiring.
또한, 본 발명에 사용되는 수지는, 중합 종료 후에 메탄올이나 물 등, 수지에 대한 빈용매 중에서 침전화한 후, 세정, 건조하여 얻을 수도 있다. 재침함으로써, 중합 시에 사용한 에스테르화제, 축합제 및 산클로라이드에 의한 부생성물이나, 수지 전구체의 저분자량 성분 등을 제거할 수 있기 때문에, 내열성이 향상되는 이점이 있다.After completion of the polymerization, the resin used in the present invention may be obtained by precipitating in a poor solvent for a resin such as methanol or water, followed by washing and drying. By repeating, the esterification agent used in the polymerization, the condensation agent, by-products of the acid chloride, and the low-molecular-weight component of the resin precursor can be removed, thereby improving the heat resistance.
본 발명의 수지는 수지 말단이 하기 일반식 (8)로 표시되는 구조를 포함하는 것이 바람직하다.The resin of the present invention preferably has a structure in which the terminal of the resin is represented by the following general formula (8).
일반식 (8) 중 R13 내지 R16은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 5의 1가의 유기기를 나타낸다.In the general formula (8), R 13 to R 16 each independently represent a halogen atom or a monovalent organic group having 1 to 5 carbon atoms.
이들 말단 구조가 포함되어 있으면, 열 처리 시에 보호기가 탈리되어 이소시아네이트기가 재생한다. 이 관능기 및 이 관능기가 가수분해되어 생긴 아미노기는 수지와 필러, 도전성 기재, 도전성 배선의 접착성을 높인다는 효과가 있다.When these terminal structures are included, the protecting group is eliminated during the heat treatment, and the isocyanate group is regenerated. This functional group and the amino group generated by hydrolysis of the functional group have the effect of enhancing the adhesion between the resin and the filler, the conductive base, and the conductive wiring.
말단 밀봉제를 갖는 수지는, 상기한 다양한 공지된 합성 방법에 있어서, 디아민, 디아소시아네이트와 산 성분을 선택적으로 조합하여 반응을 행할 때에, 먼저 디아민, 디이소시아네이트 또는 산과 반응시키고 나서, 중합 반응을 개시해도 되고, 디아민, 디이소시아네이트, 산과 동시에 혹은 그들보다 조금 지연시켜 말단 밀봉제를 첨가함으로써 얻을 수 있다.In the resin having the terminal sealing agent, in the various known synthesis methods, when a reaction is carried out by selectively combining a diamine, a diisocyanate and an acid component, the resin is first reacted with a diamine, a diisocyanate or an acid, Or may be obtained by adding the end sealant at the same time as or after the diamine, the diisocyanate, and the acid.
상기 일반식 (1), (2) 중 어느 것으로 표시되는 구조를 적어도 하나 포함하는 수지는 용제에 용해한 수지 용액으로서 사용할 수 있다.The resin containing at least one of the structures represented by the general formulas (1) and (2) can be used as a resin solution dissolved in a solvent.
본 발명의 수지 용액에 바람직하게 사용되는 용제로서는, 구체적으로는 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜디부틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르 등의 에테르류, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 프로필아세테이트, 부틸아세테이트, 이소부틸아세테이트, 3-메톡시부틸아세테이트, 3-메틸-3-메톡시부틸아세테이트, 락트산메틸, 락트산에틸, 락트산부틸 등의 아세테이트류, 아세틸아세톤, 메틸프로필케톤, 메틸부틸케톤, 메틸이소부틸케톤, 시클로펜타논, 2-헵타논 등의 케톤류, 부틸알코올, 이소부틸알코올, 펜탄올, 4-메틸-2-펜탄올, 3-메틸-2-부탄올, 3-메틸-3-메톡시부탄올, 디아세톤알코올 등의 알코올류, 톨루엔, 크실렌 등의 방향족 탄화수소류, N-메틸-2-피롤리돈, N-시클로헥실-2-피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, 디메틸술폭시드, γ-부티로락톤 등을 들 수 있다. 이들은 단독 혹은 혼합하여 사용할 수 있다.Specific examples of the solvent preferably used in the resin solution of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethers such as ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate , Acetates such as isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl Ketone, cyclopentanone, 2-heptanone, etc. Ketones, alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3- N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide,? -Butyrolactone, and the like; aromatic hydrocarbons such as N-methyl-2-pyrrolidone, And lactones. These may be used alone or in combination.
수지 용액의 농도와 점도의 범위는 농도 1 내지 50중량%이고 점도 1mPa·초 내지 1000Pa·초의 범위가 바람직하고, 보다 바람직하게는 농도 5 내지 30중량%이고 점도 100mPa·초 내지 100Pa·초이다. 이 범위임으로써, 불균일이 없는 균일한 막을 제막할 수 있다.The concentration and the viscosity of the resin solution are in the range of 1 to 50 wt% and the viscosity is preferably in the range of 1 mPa · sec to 1000 Pa · sec, more preferably 5 to 30 wt%, and the viscosity is 100 mPa · sec to 100 Pa · sec. With this range, it is possible to form a uniform film having no unevenness.
본 발명의 수지 용액은 c) 하기 일반식 (9)로 표시되는 실란 화합물을 더 포함하는 것이 바람직하다.It is preferable that the resin solution of the present invention further comprises c) a silane compound represented by the following general formula (9).
일반식 (9) 중 R17은 탄소수 1 내지 4의 알콕실기를 나타낸다. R18은 탄소수 1 내지 4의 알콕실기 또는 알킬기, R19는 탄소수 1 내지 4의 2가의 유기기를 나타낸다. 바람직한 알콕시기의 구체예로서는 메톡시기, 에톡시기, 프로폭시기, 이소프로폭시기, 부톡시기 등을 들 수 있지만 이들에 한정되지 않는다. 바람직한 알킬기의 구체예로서는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기 등을 들 수 있지만 이들에 한정되지 않는다. Z는 이소시아네이트기와 반응성이 있는 관능기를 나타낸다. 바람직한 구체예로서는 수산기, 아미노기, 에폭시기, 아크릴기, 메타크릴기, 말레이미드기, 티올기, 카르복실기, 산 무수물기, 이소시아네이트기 등을 들 수 있지만 이들에 한정되지 않는다.In the general formula (9), R 17 represents an alkoxyl group having 1 to 4 carbon atoms. R 18 represents an alkoxyl group or an alkyl group having 1 to 4 carbon atoms; and R 19 represents a divalent organic group having 1 to 4 carbon atoms. Specific examples of preferred alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like. Specific examples of preferred alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl and the like. Z represents a functional group reactive with an isocyanate group. Specific preferred examples include, but are not limited to, a hydroxyl group, an amino group, an epoxy group, an acryl group, a methacryl group, a maleimide group, a thiol group, a carboxyl group, an acid anhydride group and an isocyanate group.
특히 바람직한 화합물의 예로서는 하기에 예시한 것을 들 수 있지만 이들에 한정되지 않는다.Examples of particularly preferred compounds include, but are not limited to, those exemplified below.
3-아미노프로필트리에톡시실란, 3-아미노프로필메틸디에톡시실란, 3-아미노프로필디메틸에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필메틸디메톡시실란, 3-아미노프로필디메틸메톡시실란, 3-아미노프로필페닐디에톡시실란, 3-아미노프로필페닐디메톡시실란, 3-히드록시프로필트리에톡시실란, 3-히드록시프로필메틸디에톡시실란, 3-히드록시프로필디메틸에톡시실란, 3-히드록시프로필트리메톡시실란, 3-히드록시프로필메틸디메톡시실란, 3-히드록시프로필디메틸메톡시실란, 3-히드록시프로필페닐디에톡시실란, 3-히드록시프로필페닐디메톡시실란, 3-머캅토프로필트리에톡시실란, 3-머캅토프로필메틸디에톡시실란, 3-머캅토프로필디메틸에톡시실란, 3-머캅토프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필디메틸메톡시실란, 3-머캅토프로필페닐디에톡시실란, 3-머캅토프로필페닐디메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 3-아크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필디메틸에톡시실란, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필메틸디메톡시실란, 3-아크릴옥시프로필디메틸메톡시실란, 3-아크릴옥시프로필페닐디에톡시실란, 3-아크릴옥시프로필페닐디메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-메타크릴옥시프로필디메틸에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필디메틸메톡시실란, 3-메타크릴옥시프로필페닐디에톡시실란, 3-메타크릴옥시프로필페닐디메톡시실란, N-페닐아미노에틸트리메톡시실란, N-페닐아미노에틸트리에톡시실란, N-페닐아미노프로필트리메톡시실란, N-페닐아미노프로필트리에톡시실란, N-페닐아미노부틸트리메톡시실란, N-페닐아미노부틸트리에톡시실란 등을 들 수 있지만 이들에 한정되지 않는다 .Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiphenyldimethoxysilane, 3-aminopropylphenyldimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropyldimethylethoxy Silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropyldimethylmethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldimethoxy Silane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3-mercaptopropyldimeth 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethylsilane, 3-mercaptopropyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylphenyldiethoxysilane, 3-acryloxypropylphenyl 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3- Methacryloxypropyldimethoxysilane, 3-methacryloxypropyldimethyloxymethoxysilane, 3-methacryloxypropylphenyldiethoxysilane, 3-methacryloxypropylphenyldimethoxysilane, N-phenylaminoethyltrimethoxy Silane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, etc. But are not limited to these.
이들 실란 화합물의 함유량은, 수지 100중량부에 대하여, 0.01 내지 15중량부가 바람직하다.The content of these silane compounds is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin.
이들 실란 화합물이 포함되어 있으면, 실리콘, 티타늄, 지르코늄의 접착성이 향상되는 이점이 있고, 실리콘, 티타늄이 포함된 부극의 결합제로서 적합하게 사용할 수 있다. 특히 디이소시아네이트와 그것과 반응하는 2가 이상의 산의 반응으로 인하여 수지가 합성되는 경우는, 중합체의 말단에 존재하는 이소시아네이트와 반응하여, 말단에 접착 개량 성분이 결합한 중합체가 되어, 보다 접착 개선 효과가 증가된다는 이점이 있다.When these silane compounds are included, there is an advantage that adhesion of silicon, titanium, and zirconium is improved, and they can be suitably used as a binder for a negative electrode containing silicon and titanium. Particularly, when a resin is synthesized due to the reaction of a diisocyanate and a dihydric or higher acid reacting with the diisocyanate, the polymer reacts with the isocyanate present at the end of the polymer to form a polymer having a bonding modifying component bonded to its end, There is an advantage that it is increased.
본 발명의 수지 용액은 기능화를 위한 첨가제를 포함한 수지 조성물이어도 된다.The resin solution of the present invention may be a resin composition containing an additive for functionalization.
본 발명의 수지 조성물은 광산 발생제를 함유해도 되고, 포지티브형의 감광성을 부여할 수 있다. 광산 발생제는, 퀴논디아지드 화합물, 술포늄염 화합물, 포스포늄염 화합물, 디아조늄염 화합물, 요오도늄염 화합물 등을 들 수 있지만, 퀴논디아지드 화합물인 것이 바람직하고, 특히 o-퀴논디아지드 화합물인 것이 바람직하다. 퀴논디아지드 화합물로서는, 폴리히드록시 화합물에 퀴논디아지드의 술폰산이 에스테르로 결합한 것, 폴리아미노 화합물에 퀴논디아지드의 술폰산이 술폰아미드 결합한 것, 폴리히드록시폴리아미노 화합물에 퀴논디아지드의 술폰산이 에스테르 결합 및/또는 술폰아미드 결합한 것 등을 들 수 있다. 이들 폴리히드록시 화합물이나 폴리아미노 화합물의 모든 관능기가 퀴논디아지드로 치환되어 있지 않아도 되지만, 관능기 전체의 50몰% 이상이 퀴논디아지드로 치환되어 있는 것이 바람직하다. 50몰% 이상이 퀴논디아지드로 치환되어 있음으로써 알칼리 현상액에 대한 용해성이 양호해지고, 미노광부와의 콘트라스트가 높은 세밀한 패턴을 얻을 수 있다는 이점이 있다. 이러한 퀴논디아지드 화합물을 사용함으로써 일반적인 자외선인 수은등의 i선(365㎚), h선(405㎚), g선(436㎚)에 감광하는 포지티브형의 감광성을 갖는 수지 조성물을 얻을 수 있다.The resin composition of the present invention may contain a photoacid generator and may impart a positive photosensitivity. The photoacid generator may be a quinone diazide compound, a sulfonium salt compound, a phosphonium salt compound, a diazonium salt compound, or an iodonium salt compound, but it is preferably a quinone diazide compound, particularly an o-quinone diazide compound . As the quinone diazide compound, there may be mentioned a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, a sulfonic acid of quinone diazide in the polyhydroxypolyamino compound Ester bond and / or sulfonamide bond. Although not all the functional groups of the polyhydroxy compound and the polyamino compound may be substituted with quinone diazide, it is preferable that at least 50 mol% of the entire functional groups are substituted with quinone diazide. By substituting quinonediazide by not less than 50 mol%, the solubility in an alkali developing solution becomes good, and a fine pattern with high contrast with the unexposed portion can be obtained. By using such a quinone diazide compound, it is possible to obtain a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general ultraviolet ray.
폴리히드록시 화합물은, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, 메틸렌트리스-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, 디메틸올-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B P, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP(이상, 상품명, 혼슈 가가쿠 고교(주)제), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A(이상, 상품명, 아사히 유키자이 고교(주)제), 2,6-디메톡시메틸-4-t-부틸페놀, 2,6-디메톡시메틸-p-크레졸, 2,6-디아세톡시메틸-p-크레졸, 나프톨, 테트라히드록시벤조페논, 갈산메틸에스테르, 비스페놀 A, 비스페놀 E, 메틸렌비스페놀, BisP-AP(상품명, 혼슈 가가쿠 고교(주)제) 등을 들 수 있지만, 이들에 한정되지 않는다.Bisp-PZ, BisP-IPZ, BisP-PZ, BisP-PZ, BisP-PZ, BisP-ZZ, BisP- DML-OCHP, DML-PCHP, DML-PCC, BisRSCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-P PML, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B PML, DML-PTBP, DML-34X, DML-EP, DML- OC, BIP-PC, BIR-PC (trade name, manufactured by Honshu Kagaku Kogyo K.K.), HML-TP-BP, TML-BP- , BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Yuki- 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone Bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), and the like , But it is not limited to these.
폴리아미노 화합물은, 1,4-페닐렌디아민, 1,3-페닐렌디아민, 4,4'-디아미노디페닐에테르, 4,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐술피드 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
또한, 폴리히드록시폴리아미노 화합물은, 2,2-비스(3-아미노-4-히드록시페닐)헥사플루오로프로판, 3,3'-디히드록시벤지딘 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. Do not.
본 발명에 있어서, 퀴논디아지드는 5-나프토퀴논디아지드술포닐기, 4-나프토퀴논디아지드술포닐기 모두 바람직하게 사용된다. 4-나프토퀴논디아지드술포닐에스테르 화합물은 수은등의 i선 영역에 흡수를 갖고 있어, i선 노광에 적합하다. 5-나프토퀴논디아지드술포닐에스테르 화합물은 수은등의 g선 영역까지 흡수를 갖는 것이 신장되어, g선 노광에 적합하다. 본 발명에 있어서는, 노광하는 파장에 의해 4-나프토퀴논디아지드술포닐에스테르 화합물, 5-나프토퀴논디아지드술포닐에스테르 화합물을 선택하는 것이 바람직하다. 또한, 동일 분자 중에 4-나프토퀴논디아지드술포닐기 및 5-나프토퀴논디아지드술포닐기를 병용한, 나프토퀴논디아지드술포닐에스테르 화합물을 얻을 수도 있고, 4-나프토퀴논디아지드술포닐에스테르 화합물과 5-나프토퀴논디아지드술포닐에스테르 화합물을 병용할 수도 있다.In the present invention, quinone diazide is preferably a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidesulfonyl ester compound has absorption up to the g line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinonediazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule may be obtained, or 4-naphthoquinone diazide sulfonic acid ester A sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be used in combination.
또한, 퀴논디아지드 화합물의 분자량은 300 이상이 바람직하고, 350 이상이 보다 바람직하다. 또한, 1500 이하가 바람직하고, 1200 이하가 보다 바람직하다. 분자량이 300 이상이면 노광 감도가 높아지고, 1500 이하이면 가열 처리 후의 피막 기계 특성이 향상된다는 이점이 있다.The molecular weight of the quinone diazide compound is preferably 300 or more, more preferably 350 or more. Further, it is preferably 1500 or less, more preferably 1200 or less. When the molecular weight is 300 or more, the exposure sensitivity is high. When the molecular weight is 1500 or less, there is an advantage that the coating mechanical properties after the heat treatment are improved.
광산 발생제의 함유량은 전체적으로 수지 100중량부에 대하여 1중량부 이상이 바람직하고, 3중량부 이상이 보다 바람직하다. 또한, 50중량부 이하가 바람직하고, 40중량부 이하가 보다 바람직하다. 또한, 퀴논디아지드 화합물의 경우의 함유량은 수지 100중량부에 대하여 1중량부 이상이 바람직하고, 3중량부 이상이 보다 바람직하다. 또한, 50중량부 이하가 바람직하고, 40중량부 이하가 보다 바람직하다. 이 범위에 있으면 경화막의 기계 특성이 양호해지는 이점이 있다.The content of the photoacid generator is preferably 1 part by weight or more, more preferably 3 parts by weight or more, based on 100 parts by weight of the resin as a whole. The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. The content of the quinone diazide compound is preferably at least 1 part by weight, more preferably at least 3 parts by weight based on 100 parts by weight of the resin. The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. Within this range, there is an advantage that the mechanical properties of the cured film become good.
본 발명에 사용되는 퀴논디아지드 화합물은, 특정한 페놀 화합물로부터, 다음 방법에 의해 합성된다. 예를 들어 5-나프토퀴논디아지드술포닐클로라이드와 페놀 화합물을 트리에틸아민 존재 하에서 반응시키는 방법 등이 있다. 페놀 화합물의 합성 방법은, 산 촉매 하에서, α-(히드록시페닐)스티렌 유도체를 다가 페놀 화합물과 반응시키는 방법 등이 있다.The quinone diazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinone diazide sulfonyl chloride with a phenol compound in the presence of triethylamine. A method for synthesizing a phenol compound includes a method of reacting an? - (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.
광산 발생제 중 술포늄염 화합물, 포스포늄염 화합물, 디아조늄염 화합물로서는, 본 발명의 감광성 수지 조성물로부터 얻어지는 가열 처리 후의 피막은 영구막으로서 사용하기 때문에, 인 등이 잔존하는 것은 환경상 바람직하지 않고, 또한 막의 색조도 고려할 필요가 있는 점에서, 이들 중에서는 술포늄염이 바람직하게 사용된다. 특히 바람직한 것으로서, 트리아릴술포늄염을 들 수 있다.As the sulfonium salt compound, phosphonium salt compound and diazonium salt compound in the photoacid generator, since the film after the heat treatment obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus, etc. remain, Among these, a sulfonium salt is preferably used because it is also necessary to consider the color tone of the film. Particularly preferred are triarylsulfonium salts.
또한, 본 발명의 수지 조성물은, 네거티브형의 감광성을 부여하기 위하여, 일반식 (1) 중의 R3으로서 메타크릴산에틸기, 아크릴산에틸기, 메타크릴산프로필기, 아크릴산프로필기, 에틸메타크릴아미드기, 프로필메타크릴아미드기, 에틸아크릴아미드기, 프로필아크릴아미드기 등의 에틸렌성 불포화 이중 결합을 갖는 기를 사용할 수 있다. 또한, 수지 조성물의 감광 성능을 올리기 위하여, 광중합성 화합물을 포함해도 된다. 광중합성 화합물로서는, 2-히드록시에틸메타크릴레이트, 트리메틸올프로판트리메타크릴레이트, 트리메틸올프로판트리아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 메틸렌비스메타크릴아미드, 메틸렌비스아크릴아미드 등을 들 수 있지만, 이들에 한정되지 않는다. 광중합성 화합물은 수지 100중량부에 대하여 1 내지 30중량부의 범위에서 함유하는 것이 바람직하다. 이 범위 내이면 감도가 높고, 열 경화 후의 막 기계 특성도 양호한 조성물이 된다. 이들 광중합성 화합물은, 단독으로 혹은 2종 이상 사용할 수 있다.In addition, the resin composition of the present invention may contain, as R 3 in the general formula (1), an ethyl methacrylate group, an ethyl acrylate group, a propyl methacrylate group, a propyl acrylate group, an ethyl methacrylamide group , A group having an ethylenically unsaturated double bond such as a propyl methacrylamide group, an ethyl acrylamide group and a propyl acrylamide group. In order to increase the photosensitive performance of the resin composition, a photopolymerizable compound may be included. Examples of the photopolymerizable compound include 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate Propylene glycol dimethacrylate, methylenebismethacrylamide, methylenebisacrylamide, and the like, but are not limited thereto. The photopolymerizable compound is preferably contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin. Within this range, a composition having high sensitivity and good film-forming properties after heat curing can be obtained. These photopolymerizable compounds may be used alone or in combination of two or more.
또한, 본 발명의 수지 조성물에 네거티브형의 감광성을 부여하는 경우, 광중합 개시제를 함유해도 된다. 본 발명에 적합한 광중합 개시제로서는, N-페닐디에탄올아민, N-페닐글리신 등의 방향족 아민류, 미힐러 케톤 등의 방향족 케톤류, 3-페닐-5-이소옥사졸론으로 대표되는 환상 옥심 화합물, 1-페닐프로판디온-2-(o-에톡시카르보닐)옥심으로 대표되는 쇄상 옥심 화합물, 벤조페논, o-벤조일벤조산메틸, 디벤질케톤, 플루오레논 등의 벤조페논 유도체, 티오크산톤, 2-메틸티오크산톤, 2-이소프로필티오크산톤 등의 티오크산톤 유도체 등을 들 수 있지만, 이들에 한정되지 않는다.When a negative type photosensitive property is imparted to the resin composition of the present invention, a photopolymerization initiator may be contained. Examples of the photopolymerization initiator suitable for the present invention include aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michler's ketone, cyclic oxime compounds represented by 3-phenyl-5-isoxazolone, 1- Chain oxime compounds represented by phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzyl ketone and fluorenone, thioxanthone, 2- Thioxanthone derivatives such as thioxanthone and 2-isopropylthioxanthone, and the like, but the present invention is not limited thereto.
광중합 개시제의 함유량은, 수지 100중량부에 대하여 0.01중량부 이상이 바람직하고, 0.1중량부 이상이 보다 바람직하다. 또한, 30중량부 이하가 바람직하고, 20중량부 이하가 보다 바람직하다. 이 범위 내이면 감도도 높고, 열 경화 후의 막 기계 특성도 양호한 조성물이 된다. 이들 광 개시제는, 단독으로, 혹은 2종 이상 사용할 수 있다.The content of the photopolymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the resin. The content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. Within this range, the composition is high in sensitivity and good in film mechanical properties after heat curing. These photoinitiators may be used alone or in combination of two or more.
또한 네거티브형의 감광 특성을 향상시키기 위하여 광 증감제를 포함하는 것이 보다 바람직하다. 본 발명에 적합한 광 증감제로서는, 아지드안트라퀴논, 아지드벤잘아세토페논 등의 방향족 모노아지드, 7-디에틸아미노벤조일쿠마린, 3,3'-카르보닐비스(디에틸아미노쿠마린) 등의 아미노쿠마린류, 벤즈안트론, 페난트렌퀴논 등의 방향족 케톤류 등, 일반적으로 광 경화성 수지에 사용되는 것을 들 수 있다. 기타 전자 사진 감광체의 전하 이동제로서 사용되는 것이면 바람직하게 사용할 수 있는 경우도 있다.Further, it is more preferable to include a photosensitizer in order to improve the negative type photosensitive characteristics. Examples of the photosensitizer suitable for the present invention include aromatic monoazides such as azide anthraquinone and azidobenzalacetophenone, 7-diethylaminobenzoyl coumarin, 3,3'-carbonylbis (diethylaminocoumarin) And aromatic ketones such as aminocoumarins, benzanthrone, phenanthrenequinone, and the like, which are generally used for photocurable resins. And may be preferably used if it is used as a charge transfer agent for other electrophotographic photosensitive members.
광 증감제의 함유량은, 수지 100중량부에 대하여 0.01중량부가 바람직하고, 0.1중량부 이상이 보다 바람직하다. 또한, 30중량부 이하가 바람직하고, 20중량부 이하가 보다 바람직하다. 이 범위 내이면 감도도 높고, 가열 처리 후의 피막 기계 특성도 양호한 조성물이 된다. 이들 광 증감제는, 단독으로, 혹은 2종 이상 사용할 수 있다.The content of the photosensitizer is preferably 0.01 parts by weight, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the resin. The content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. Within this range, the composition becomes a composition having high sensitivity and good film-forming properties after the heat treatment. These photosensitizers may be used alone or in combination of two or more.
본 발명의 수지 조성물은, 수지 조성물로 형성되는 수지막의 알칼리 현상성을 제어할 목적으로, 페놀성 수산기를 갖는 화합물을 함유할 수 있다.The resin composition of the present invention may contain a compound having a phenolic hydroxyl group for the purpose of controlling the alkali developability of the resin film formed of the resin composition.
본 발명에서 사용할 수 있는 페놀성 수산기를 갖는 화합물로서는, 예를 들어Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA(테트라키스 P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, 메틸렌트리스-FR-CR, BisRS-26X, BisRS-OCHP(이상, 상품명, 혼슈 가가쿠 고교(주)제), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A(이상, 상품명, 아사히 유키자이 고교(주)제)를 들 수 있다.Examples of the compound having a phenolic hydroxyl group that can be used in the present invention include bis-Z, BisOC-Z, BisOP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP- BisP-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P- BisPC-OCHP, Bis26-OCHP, BisOCHP-OC, Bis236T-OCHP, BisPC-OCHP, BisPC-OCHP, BisPC- BIR-PC, BIR-PCB, BIR-PCHP, BIP-PCB, and BIS-OCHP (all trade names, manufactured by Honshu Chemical Industries, Ltd.) -BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (all trade names, manufactured by Asahi Yuki Kai Kogyo Co., Ltd.).
이들 중 바람직한 페놀성 수산기를 갖는 화합물로서는, 예를 들어 Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, 메틸렌트리스-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F 등을 들 수 있다. 이들 중 특히 바람직한 페놀성 수산기를 갖는 화합물로서는, 예를 들어 Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F이다. 이 페놀성 수산기를 갖는 화합물을 함유함으로써, 얻어지는 수지 조성물은, 노광 전은 알칼리 현상액에 용이하게 용해되고, 노광되면 알칼리 현상액에 난용이 되며, 또한 현상에 의한 막 감소가 적고, 단시간에 현상이 용이해진다.Among these, preferred compounds having a phenolic hydroxyl group include bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP- BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, and the like, as well as bisCOP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- . Among these compounds, particularly preferred compounds having a phenolic hydroxyl group are Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS- -F. By containing the compound having a phenolic hydroxyl group, the resulting resin composition is easily dissolved in an alkaline developer before exposure, becomes unstable in an alkaline developer when exposed, has less film loss due to development, and is easy to develop in a short time It becomes.
이러한 페놀성 수산기를 갖는 화합물의 함유량은, 수지 100중량부에 대하여, 바람직하게는 1 내지 60중량부이며, 보다 바람직하게는 3 내지 50중량부의 범위이다.The content of the compound having a phenolic hydroxyl group is preferably from 1 to 60 parts by weight, more preferably from 3 to 50 parts by weight, based on 100 parts by weight of the resin.
본 발명의 수지 조성물은, 가열 처리 후의 피막의 실리콘, 질화실리콘, 산화실리콘 및 인실리케이트 유리 등의 실리콘계 기판, ITO 기판과의 접착성을 보다 높이거나, 세정 등에 사용되는 산소 플라스마, UV 오존 처리에 대한 내성을 높이기 위하여, 일반식 (8)로 표시되는 실란 화합물 이외의 실란 커플링제, 티타늄킬레이트제, 알루미늄킬레이트제 등을 함유할 수도 있다. 바람직한 실란 커플링제의 구체예로서는, 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리클로로실란, 비닐트리스(β-메톡시에톡시)실란 등을 들 수 있다.The resin composition of the present invention can be applied to a silicon substrate such as silicon, silicon nitride, silicon oxide and phosphoric silicate glass of a film after heat treatment, oxygen plasma used for cleaning or the like, adhesion to an ITO substrate, A silane coupling agent other than the silane compound represented by the general formula (8), a titanium chelating agent, an aluminum chelating agent and the like may be contained in order to enhance the resistance to heat. Specific examples of preferred silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane, and the like.
이들 접착 개량제의 함유량은, 수지 100중량부에 대하여, 0.01 내지 15중량부가 바람직하다.The content of the adhesion improver is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin.
또한, 수지 조성물을 도포하는 기판 표면을 미리 전처리함으로써, 접착성을 더욱 향상시키는 것도 가능하다. 전처리의 방법으로서는, 예를 들어 다음과 같은 방법을 들 수 있다. 상기에서 설명한 접착 개량제를 이소프로판올, 에탄올, 메탄올, 물, 테트라히드로푸란, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노메틸에테르, 락트산에틸, 아디프산디에틸 등의 용매에 0.5 내지 20중량부 용해시킨 용액을 스핀 코팅, 침지, 스프레이 도포, 증기 처리 등으로 표면 처리를 한다. 또한, 헥사메틸디실라잔 증기를 직접 분무하여 처리해도 된다. 그 후, 필요에 따라 감압 건조 처리를 실시하고, 50 내지 300℃까지의 온도를 가함으로써, 실리콘계 재료 표면과 상기 접착 개량제의 반응을 진행시킨다.It is also possible to further improve the adhesiveness by pretreating the surface of the substrate to which the resin composition is applied in advance. As a method of the pretreatment, for example, the following method can be mentioned. A solution prepared by dissolving 0.5 to 20 parts by weight of the above-described improving agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray application, steam treatment, or the like. Further, the hexamethyldisilazane vapor may be directly spray-treated. Thereafter, a vacuum drying treatment is carried out if necessary, and a temperature of 50 to 300 ° C is applied to advance the reaction between the surface of the silicon-based material and the above-mentioned adhesion improver.
본 발명의 수지 조성물은, 계면 활성제를 함유해도 되어, 기판과의 습윤성을 향상시킬 수 있다.The resin composition of the present invention may contain a surfactant, which can improve the wettability with the substrate.
계면 활성제로서는, "플로라드"(등록 상표)(상품명, 스미토모 3M(주)제), "메가페이스"(등록 상표)(상품명, DIC(주)제), "술푸론"(등록 상표)(상품명, 아사히 가라스(주)제) 등의 불소계 계면 활성제, KP341(상품명, 신에쓰 가가꾸 고교(주)제), DBE(상품명, 칫소(주)제), "글라놀"(등록 상표)(상품명, 교에이샤 가가꾸(주)제), BYK(빅·케미(주)제) 등의 유기 실록산 계면 활성제, "폴리플로우"(등록 상표)(상품명, 교에이샤 가가꾸(주)제) 등의 아크릴 중합물 계면 활성제 등을 들 수 있다.Examples of the surfactant include fluoride (registered trademark) (trade name, manufactured by Sumitomo 3M Ltd.), megaface (registered trademark) (trade name, manufactured by DIC Corporation), sulfulfone (registered trademark) Fluorine surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.) (Trade name, produced by Kyoeisha Chemical Co., Ltd.) and BYK (manufactured by Big Chemie Co., Ltd.), and organic siloxane surfactants such as "Polyflow" And the like), and the like.
본 발명의 수지 용액에, 필러를 첨가하여 슬러리로서도 사용할 수도 있다. 반도체, 디스플레이, 다층 배선 기판에 사용하는 경우는, 필러를 첨가함으로써, 한층 더한 저선팽창화, 고강도화나 굴절률, 유전율, 투자율의 제어를 기대할 수 있다. 2차 전지나 캐패시터에 사용하는 경우는 정극, 부극으로서의 기능화가 가능해진다.A filler may be added to the resin solution of the present invention and used as a slurry. When used in semiconductors, displays, and multilayer wiring boards, the addition of a filler makes it possible to achieve further lower linear expansion and higher strength, control of refractive index, permittivity and permeability. When used in a secondary battery or a capacitor, functionalization as a positive electrode and a negative electrode becomes possible.
반도체, 디스플레이, 다층 배선 기판에 사용하는 경우의 바람직한 필러로서는, 산화실리콘, 산화티타늄, 알루미나, 티타늄산바륨, 질화알루미늄, 산화지르코늄, 질화실리콘, 질화티타늄 등을 들 수 있지만 이들에 한정되지 않는다.Silicon oxide, titanium oxide, alumina, barium titanate, aluminum nitride, zirconium oxide, silicon nitride, titanium nitride, and the like are preferable fillers for use in semiconductors, displays, and multilayer wiring boards, but the present invention is not limited thereto.
2차 전지나 캐패시터에 사용하는 경우의 바람직한 필러로서는, 탄소, 실리콘, 주석, 게르마늄, 티타늄, 철, 코발트, 니켈, 망간, 구리, 은, 아연, 인듐, 비스무트, 안티몬 또는 크롬 등의 원자를 포함하는 화합물을 들 수 있다. 바람직하게는, 탄소, 망간, 코발트, 니켈, 철, 실리콘, 티타늄, 주석 및 게르마늄 중 적어도 1종류의 원자를 포함하는 화합물이며, 보다 바람직하게는 실리콘, 티타늄 중 적어도 1종류의 원자를 포함하는 화합물이다.Preferred fillers for use in secondary batteries and capacitors are those containing atoms such as carbon, silicon, tin, germanium, titanium, iron, cobalt, nickel, manganese, copper, silver, zinc, indium, bismuth, antimony or chromium Compounds. Preferably, a compound containing at least one atom of carbon, manganese, cobalt, nickel, iron, silicon, titanium, tin and germanium, more preferably a compound containing at least one atom of silicon and titanium to be.
이들 화합물을 필러로서 사용하면, 필러가 활물질로서의 역할을 한다. 이로인해, 본 발명의 수지에 필러를 첨가하여, 슬러리로 함으로써, 이차 전지나 캐패시터의 전극용 슬러리로서 사용할 수 있다.When these compounds are used as a filler, the filler serves as an active material. As a result, the slurry can be used as a slurry for an electrode of a secondary battery or a capacitor by adding a filler to the resin of the present invention.
또한, 정극용의 필러의 예로서는, 인산철리튬, 코발트산리튬, 니켈산리튬, 망간산리튬, 활성탄, 카본 나노튜브 등을 들 수 있다.Examples of the positive electrode filler include lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, activated carbon, and carbon nanotubes.
또한, 부극용의 필러의 예로서는, 티타늄산리튬, 하드 카본, 소프트 카본, 활성탄, 카본 나노튜브, 실리콘, 주석, 게르마늄 원자를 포함하는 화합물 등을 들 수 있다. 특히, 실리콘, 주석, 게르마늄 원자를 포함하는 화합물을 필러로서 사용한 축전지는, 충전 시에 활물질의 부피 팽창이 크기 때문에, 본 발명의 수지와 같은 기계 강도가 높은 수지를 결합제로서 사용하는 것이 활물질의 열화, 나아가, 충방전 시의 용량 열화를 저감시키는 데 있어서 바람직하다.Examples of the negative electrode filler include lithium titanate, hard carbon, soft carbon, activated carbon, carbon nanotubes, silicon, tin, and compounds containing germanium atoms. Particularly, a battery using a compound containing silicon, tin, and germanium atoms as a filler has a large volume expansion of the active material at the time of charging. Therefore, when a resin having high mechanical strength such as the resin of the present invention is used as a binder, And further, it is preferable to reduce the capacity deterioration at the time of charge / discharge.
규소 원자를 포함하는 화합물로서는, 예를 들어 (1) 실리콘 미립자, (2) 주석, 니켈, 구리, 철, 코발트, 망간, 아연, 인듐, 은, 티타늄, 게르마늄, 비스무트, 안티몬 또는 크롬과, 규소와의 합금 (3) 붕소, 질소, 산소 또는 탄소와 규소와의 화합물이나, 이들에 (2)에 예시한 금속을 더 갖는 것 등을 들 수 있다. 규소의 합금 혹은 화합물의 일례로서는, SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu5Si, FeSi2, MnSi2, NbSi2, TaSi2, VSi2, WSi2, ZnSi2, SiC, Si3N4, Si2N2O, SiOv(0<v≤2) 혹은 LiSiO 등을 들 수 있다.Examples of the compound containing silicon atom include (1) silicon fine particles, (2) tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, (3) a compound of boron, nitrogen, oxygen, or carbon and silicon, and a metal further having a metal exemplified in (2). As an example of the alloy or compound of silicon, SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi 2 , NbSi 2 , TaSi 2 , VSi 2 , WSi 2 , ZnSi 2 , SiC, Si 3 N 4 , Si 2 N 2 O, SiOv (0 <v≤2), or LiSiO.
주석 원자를 포함하는 화합물로서는, 예를 들어 (1) 규소, 니켈, 구리, 철, 코발트, 망간, 아연, 인듐, 은, 티타늄, 게르마늄, 비스무트, 안티몬 또는 크롬과, 주석과의 합금, (2) 산소 또는 탄소와 주석과의 화합물이나, 이들에 (1)에 예시한 금속을 더 갖는 것 등을 들 수 있다. 주석의 합금 혹은 화합물의 일례로서는, SnOw(0<w≤2), SnSiO3, LiSnO 혹은 Mg2Sn 등을 들 수 있다.Examples of the compound containing a tin atom include (1) an alloy of tin with silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, ) Oxygen or a compound of carbon and tin, and those having a metal further exemplified in (1). Examples of alloys or compounds of tin include SnOw (0 < w? 2), SnSiO 3 , LiSnO, Mg 2 Sn and the like.
게르마늄 원자를 포함하는 화합물로서는, 규소나 주석과 게르마늄과의 합금 등을 들 수 있다.Examples of the compound containing a germanium atom include an alloy of silicon and tin and germanium.
필러의 입도 분포에서의 메디안 직경(d50)은 0.01 내지 20㎛가 바람직하다. 또한, 필러의 표면에는, 실란 커플링제 등에 의한 처리가 실시되어 있어도 된다.The median diameter d50 in the particle size distribution of the filler is preferably 0.01 to 20 mu m. The surface of the filler may be treated with a silane coupling agent or the like.
여기서, 메디안 직경은 호리바 세이사쿠쇼제 레이저 회절/산란식 입도 분포 측정 장치 LA-920을 사용하여 측정했다. 측정 전에, 적량의 시료를 헥사메타인산 Na 수용액에 첨가하고, 초음파 세정기로 10분 정도 분산시키고, 그 후 측정을 행했다. 이에 의해, 분체가 응집된 시료에서는 응집을 풀고, 또한 입경이 큰 분체의 침전 등을 억제하여, 정확한 입도 분포의 측정이 가능해진다.Here, the median diameter was measured using a laser diffraction / scattering type particle size distribution measuring apparatus LA-920 manufactured by Horiba Seisakusho Co., Ltd. Before measurement, an appropriate amount of a sample was added to an aqueous solution of sodium hexametaphosphate and dispersed by an ultrasonic cleaner for about 10 minutes, and then measurement was carried out. As a result, in the sample in which the powder is agglomerated, the agglomeration is released and the precipitation of the powder having a large particle size is suppressed, and the accurate particle size distribution can be measured.
본 발명의 슬러리에 있어서, 수지(첨가제가 첨가되어 있는 경우는 수지+첨가제)의 함유량은, 필러 100중량부에 대하여 1중량부 이상이 바람직하고, 접착성을 보다 향상시킬 수 있다. 3중량부 이상이 보다 바람직하고, 5중량부 이상이 더욱 바람직하다.In the slurry of the present invention, the content of the resin (resin + additive in the case where the additive is added) is preferably 1 part by weight or more based on 100 parts by weight of the filler, and the adhesion can be further improved. More preferably 3 parts by weight or more, and still more preferably 5 parts by weight or more.
2차 전지나 캐패시터의 전극에 사용하는 경우, 전기 저항을 저감시키고, 필러의 충전량을 증가시키기 위해서는 20중량부 이하가 바람직하고, 15중량부 이하가 보다 바람직하고, 12중량부 이하가 가장 바람직하다.When it is used for an electrode of a secondary battery or a capacitor, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and most preferably 12 parts by weight or less, in order to reduce electric resistance and increase the filling amount of the filler.
2차 전지나 캐패시터의 전극에 사용하는 경우, 전기 저항을 저하시키기 위하여, 본 발명의 부극용 페이스트에, 그래파이트, 케첸 블랙, 카본 나노튜브, 아세틸렌 블랙 등의 도전성 입자를 함유해도 된다. 이들의 함유량은, 부극 활물질 100중량부에 대하여 0.1중량부 이상 20중량부 이하가 바람직하다.When used for an electrode of a secondary battery or a capacitor, conductive particles such as graphite, ketjen black, carbon nanotube, and acetylene black may be contained in the negative electrode paste of the present invention in order to lower the electrical resistance. The content thereof is preferably 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the negative electrode active material.
본 발명의 수지 용액, 수지 조성물, 슬러리는, 수지, 필요에 따라 용제 및 기타 첨가제를 혼합·혼련함으로써 얻을 수 있다. 혼합의 경우는 유리제 플라스크나 스테인리스제의 용기 등에 넣고, 메커니컬 교반기 등에 의해 교반 용해시키는 방법, 초음파로 용해시키는 방법, 유성식 교반 탈포 장치로 교반 용해시키는 방법 등을 들 수 있고, 혼련의 경우는 플라네터리 믹서, 3축 롤, 볼 밀, 호모지나이저 등을 사용한 방법을 들 수 있다. 혼합·혼련의 조건에 대해서는 특별히 한정되지 않는다.The resin solution, the resin composition and the slurry of the present invention can be obtained by mixing and kneading a resin, a solvent and other additives as required. Examples of the mixing method include a method of dissolving in a glass flask or a container made of stainless steel by means of a mechanical stirrer or the like, a method of dissolving by ultrasonic waves, a method of dissolving with stirring by a planetary stirring defoaming device, A rotary mixer, a three-axis roll, a ball mill, a homogenizer, and the like. The conditions of mixing and kneading are not particularly limited.
또한, 이물을 제거하기 위하여 혼합, 혼련 후의 수지 용액, 수지 조성물, 슬러리를 0.01㎛ 내지 100㎛의 포어 사이즈의 필터로 여과해도 된다. 여과 필터의 재질에는 폴리프로필렌(PP), 폴리에틸렌(PE), 나일론(NY), 폴리테트라플루오로에틸렌(PTFE) 등이 있지만, 폴리에틸렌이나 나일론이 바람직하다. 또한, 수지 조성물 중에 필러, 유기 안료를 함유하는 경우, 이들 입자 직경보다 큰 구멍 직경의 여과 필터를 사용하는 것이 바람직하다.Further, the resin solution, the resin composition, and the slurry after mixing and kneading may be filtered with a pore size filter of 0.01 mu m to 100 mu m in order to remove foreign matter. Examples of the material of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Polyethylene and nylon are preferred. When the resin composition contains a filler or an organic pigment, it is preferable to use a filter having a pore diameter larger than the particle diameter.
본 발명의 수지 용액, 수지 조성물 또는 슬러리를 기재의 편면 또는 양면에 도포하고, 건조시킴으로써 적층체를 만들 수도 있다.A resin solution, a resin composition or a slurry of the present invention may be applied to one side or both sides of a substrate and dried to form a laminate.
기재에는 도전성 기재나, 도전성의 배선이 형성된 절연 기재가 사용된다. 도전성 기재, 배선으로서 바람직한 것은 구리, 알루미늄, 스테인리스, 니켈, 금, 은이나 그들의 합금, 카본 등이지만 이들에 한정되지 않는다. 특히 구리, 알루미늄, 금, 니켈과 그들을 포함한 합금이 보다 바람직하다. 절연 기재로서는 PET, 폴리이미드, 폴리벤조옥사졸, 폴리아미드, 폴리아미드이미드, 에폭시와 같은 유기 기재나, 산화실리콘, 질화실리콘, 질화티타늄, 산화티타늄 및 그들이 도포면에 형성된 기재 등을 들 수 있지만 이들에 한정되지 않는다.As the substrate, a conductive substrate or an insulating substrate having a conductive wiring is used. Preferred examples of the conductive substrate and the wiring include copper, aluminum, stainless steel, nickel, gold, silver and alloys thereof, carbon, and the like, but are not limited thereto. Particularly, copper, aluminum, gold, nickel and alloys including them are more preferable. Examples of the insulating substrate include organic substrates such as PET, polyimide, polybenzoxazole, polyamide, polyamideimide and epoxy, silicon oxide, silicon nitride, titanium nitride, titanium oxide and a substrate formed on a coating surface thereof. .
본 발명의 적층체 제조 방법에 대하여 설명한다.The method for producing a laminate of the present invention will be described.
먼저, 본 발명의 수지 용액, 수지 조성물 또는 슬러리를 기재 위에 도포한다.First, the resin solution, the resin composition or the slurry of the present invention is applied onto the substrate.
도포 방법으로서는 롤 코터, 슬릿 다이 코터, 바 코터, 콤마 코터, 스핀 코터 등을 사용하는 방법을 들 수 있다. 또한, 도포막 두께는, 도포 방법, 조성물의 고형분 농도, 점도 등에 따라 상이하지만, 통상 건조 후의 막 두께가 0.1 내지 150㎛인 것이 바람직하다.As a coating method, there can be mentioned a method using a roll coater, a slit die coater, a bar coater, a comma coater, a spin coater and the like. The thickness of the coating film is preferably from 0.1 to 150 mu m after drying, though it differs depending on the coating method, solid concentration of the composition, viscosity, and the like.
다음에 도포한 기판을 건조하여, 수지 조성물 피막을 얻는다. 건조는 오븐, 핫 플레이트, 적외선 등을 사용하고, 50℃ 내지 200℃의 범위에서 1분간 내지 수시간 행하는 것이 바람직하다.Next, the coated substrate is dried to obtain a resin composition film. The drying is preferably carried out in an oven, a hot plate, an infrared ray or the like at a temperature of 50 to 200 DEG C for 1 minute to several hours.
수지 용액, 수지 조성물 또는 슬러리가 감광성인 경우는 피막에 원하는 패턴을 갖는 마스크를 통하여 화학선을 조사하여, 노광한다. 노광에 사용되는 화학선으로서는 자외선, 가시광선, 전자선, X선 등이 있지만, 본 발명에서는 파장 350㎚ 이상 450㎚ 이하의 광이 바람직하고, 수은등의 i선(파장 365㎚), h선(파장 405㎚), g선(파장 436㎚)을 사용하는 것이 바람직하다.When the resin solution, the resin composition, or the slurry is photosensitive, the coating film is exposed to actinic rays through a mask having a desired pattern and exposed. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, light having a wavelength of 350 nm or more and 450 nm or less is preferable, and an i-line (wavelength 365 nm) 405 nm) and g-line (wavelength: 436 nm) are preferably used.
또한, 감광성이 아닌 수지 용액, 수지 조성물 또는 슬러리를 노광하는 경우는, 수지 피막 위에 추가로 1층 더 포토레지스트 피막을 형성시킬 필요가 있다. 이 포토레지스트에는 OFPR-800(도쿄 오카(주)제) 등의 일반적인 노볼락계 레지스트가 바람직하게 사용된다. 포토레지스트 피막의 형성은 수지 조성물 피막의 형성과 마찬가지의 방법으로 행해진다.When a resin solution, a resin composition or a slurry which is not photosensitive is exposed, it is necessary to further form one photoresist film on the resin film. As the photoresist, a typical novolac-based resist such as OFPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is preferably used. The formation of the photoresist coating is carried out in the same manner as the formation of the resin composition coating.
현상 시의 패턴의 해상도가 향상되는 경우, 현상 조건의 허용폭이 증대되는 경우에는, 현상 전에 베이크 처리를 하는 공정을 도입해도 지장없다. 이 온도로서는 50 내지 180℃의 범위가 바람직하고, 특히 60 내지 150℃의 범위가 보다 바람직하다. 시간은 10초 내지 수 시간이 바람직하다. 이 범위 내이면 반응이 양호하게 진행되고, 현상 시간도 짧아도 된다는 이점이 있다.In the case where the resolution of the pattern at the time of development is improved and the allowable width of the developing condition is increased, the step of baking before development may be introduced. The temperature is preferably in the range of 50 to 180 占 폚, more preferably in the range of 60 to 150 占 폚. The time is preferably 10 seconds to several hours. Within this range, the reaction proceeds well and the development time can be shortened.
수지 용액, 수지 조성물 또는 슬러리의 패턴을 형성하기 위해서는, 현상 처리를 행한다. 수지 용액, 수지 조성물 또는 슬러리가 네거티브형 감광성을 갖는 경우, 미노광부를 현상액으로 제거함으로써, 포지티브형 감광성을 갖는 경우, 노광부를 현상액으로 제거함으로써 릴리프·패턴이 얻어진다.In order to form a pattern of the resin solution, the resin composition or the slurry, development processing is performed. In the case where the resin solution, the resin composition or the slurry has a negative type photosensitive property, the unexposed portion is removed with a developer, and in the case of having a positive type photosensitive, the relief pattern is obtained by removing the exposed portion with a developer.
현상액은 수지의 구조에 맞게 적당한 것을 선택할 수 있지만, 암모니아, 수산화테트라메틸암모늄의 수용액, 디에탄올아민, 디에틸아미노에탄올, 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산칼륨, 트리에틸아민, 디에틸아민, 메틸아민, 디메틸아민, 아세트산디메틸아미노에틸, 디메틸아미노에탄올, 디메틸아미노에틸메타크릴레이트, 시클로헥실아민, 에틸렌디아민, 헥사메틸렌디아민 등의 알칼리성을 나타내는 화합물의 수용액을 바람직하게 사용할 수 있다. 경우에 따라서는, 이들 알칼리 수용액에 N-메틸-2-피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, 디메틸술폭시드, γ-부티로락톤, 디메틸아크릴아미드 등의 극성 용매, 메탄올, 에탄올, 이소프로판올 등의 알코올류, 락트산에틸, 프로필렌글리콜모노메틸에테르아세테이트 등의 에스테르류, 시클로펜타논, 시클로헥사논, 이소부틸케톤, 메틸이소부틸케톤 등의 케톤류 등을 1종 이상 첨가해도 된다.The developing solution may be selected appropriately in accordance with the structure of the resin, but it is preferable to use an aqueous solution of ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, An aqueous solution of an alkaline compound such as methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like can be preferably used. In some cases, these alkaline aqueous solutions may be mixed with an aqueous solution of an alkali such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Polar solvents, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, Or more.
또한, 현상액으로서 본 발명의 수지 양용매인 N-메틸-2-피롤리돈, N-아세틸-2-피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, 디메틸술폭시드, 헥사메틸포스포르트리아미드 등이나, 수지의 빈용매인 메탄올, 에탄올, 이소프로필알코올, 물, 메틸카르비톨, 에틸카르비톨, 톨루엔, 크실렌, 락트산에틸, 피루브산에틸, 프로필렌글리콜모노메틸에테르아세테이트, 메틸-3-메톡시프로피오네이트, 에틸-3-에톡시프로피오네이트, 2-헵타논, 시클로펜타논, 시클로헥사논, 아세트산에틸 등을 단독 혹은 수 종류로 상기 양용매와 조합한 혼합액도 바람직하게 사용할 수 있다.Further, as a developing solution, there may be used a solution prepared by dissolving N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Hexamethylphosphoric triamide, and hexamethylphosphoric triamide; or a poor solvent of resins such as methanol, ethanol, isopropyl alcohol, water, methylcarbitol, ethylcarbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, and ethyl acetate alone or in combination with the above- Can be used.
현상은 상기한 현상액을 도막면에 그대로, 혹은 안개 상태로서 방사하거나, 현상액 중에 침지하거나, 혹은 침지하면서 초음파를 가하는 등의 방법에 의해 행할 수 있다.The development can be carried out by a method such as irradiating the above developer directly on the coated film surface, as a misty state, immersing in a developer, or applying ultrasonic waves while dipping.
계속해서 린스액에 의해, 현상에 의해 형성한 릴리프·패턴을 세정하는 것이 바람직하다. 린스액으로서는, 현상액에 알칼리 수용액을 사용한 경우, 물을 바람직하게 사용할 수 있다. 이때, 에탄올, 이소프로필알코올류, 프로필렌글리콜모노메틸에테르아세테이트 등의 에스테르류, 탄산 가스, 염산, 아세트산 등의 산 등을 물에 첨가하여 린스 처리를 해도 된다.It is then preferable to clean the relief pattern formed by the development with the rinsing liquid. As the rinse liquid, when an alkali aqueous solution is used for the developer, water can be preferably used. At this time, esters such as ethanol, isopropyl alcohol, and propylene glycol monomethyl ether acetate, acid such as carbonic acid gas, hydrochloric acid, and acetic acid may be added to water and rinsed.
유기 용매로 린스를 하는 경우, 현상액과의 혼화성이 좋은 메탄올, 에탄올, 이소프로필알코올, 락트산에틸, 피루브산에틸, 프로필렌글리콜모노메틸에테르아세테이트, 메틸-3-메톡시프로피오네이트, 에틸-3-에톡시프로피오네이트, 2-헵타논, 아세트산에틸 등이 바람직하게 사용된다.In case of rinsing with an organic solvent, it is preferable to use methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propyleneglycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl- Ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.
수지 용액, 수지 조성물 또는 슬러리에 감광성이 부여되어 있지 않은 경우는, 현상 후에 수지막 위에 형성된 포토레지스트 피막의 제거를 행해야 한다. 이 제거는 건식 에칭에 의한 제거, 내지는 박리 용제에 의한 습식 에칭 등으로 행하여지는 경우가 많다. 상기 박리 용제로서는, 아세톤, 아세트산부틸, 락트산에틸, 프로필렌글리콜모노메틸에테르아세테이트, 메틸-3-메톡시프로피오네이트, 에틸-3-에톡시프로피오네이트, 2-헵타논, 아세트산에틸 등의 유기 용제나, 수산화나트륨, 수산화칼륨의 수용액 등이 사용되지만 이들에 한정되지 않는다.If the resin solution, the resin composition or the slurry is not provided with photosensitivity, the photoresist film formed on the resin film after development should be removed. This removal is often performed by removal by dry etching or wet etching by a peeling solvent. Examples of the peeling solvent include organic solvents such as acetone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, A solvent, an aqueous solution of sodium hydroxide, potassium hydroxide, or the like is used, but is not limited thereto.
내열성을 더욱 향상시키기 위하여, 현상 후에 150℃ 내지 500℃의 온도에서 큐어해도 된다. 를 가하여 내열성 피막으로 변환한다. 이 가열 처리는 온도를 선택하여, 단계적으로 승온하거나, 어느 온도 범위를 선택하여 연속적으로 승온하면서 5분간 내지 5시간 실시하는 것이 바람직하다. 일례로서는, 130℃, 200℃, 350℃에서 각 30분간씩 열 처리하는 방법, 실온부터 320℃까지 2시간에 걸쳐 직선적으로 승온하는 방법 등을 들 수 있다. 또한, 고온의 가열이나 그 반복에 의해, 소자의 전기 특성이 변화될 우려나, 기판의 휨이 커질 우려가 있기 때문에, 가열 처리는 250℃ 이하에서 행하여지는 것이 바람직하다. 특히 일반식 (2)로 표시되는 수지는 이미 환상 구조를 갖고 있기 때문에, 가열 처리 온도를 고온으로 하여 탈수 폐환할 필요가 없으므로 200℃ 이하의 저온 처리가 가능해지는 것이 최대의 이점이다.In order to further improve the heat resistance, it may be cured at a temperature of 150 ° C to 500 ° C after development. To the heat-resistant film. This heat treatment is preferably carried out by selecting the temperature, raising the temperature stepwise, or selecting the temperature range and continuously raising the temperature for 5 minutes to 5 hours. As an example, there are a method of performing heat treatment at 130 ° C, 200 ° C, and 350 ° C for 30 minutes each, and a method of linearly raising the temperature from room temperature to 320 ° C over 2 hours. In addition, since the electrical characteristics of the device may be changed by heating at high temperature or by repetition thereof, and the warpage of the substrate may increase, the heat treatment is preferably performed at 250 캜 or lower. In particular, since the resin represented by the general formula (2) already has a cyclic structure, it is not necessary to carry out dehydration cyclization at a high temperature for the heat treatment.
이어서, 본 발명의 리튬 이온 전지 전극, 전기 2중층 캐패시터 전극의 제조 방법에 대하여 예를 들어 설명한다.Next, a method of manufacturing the lithium ion battery electrode and the electric double layer capacitor electrode of the present invention will be described by way of example.
리튬 이온 전지 부극(이하, 부극이라고 칭하는 경우가 있음)의 경우, 본 발명의 슬러리를 금속박 위에 1 내지 100㎛의 두께로 도포한다. 금속박으로서는, 구리박이 일반적으로 사용된다. 도포에는 스크린 인쇄, 롤 코팅, 슬릿 코팅 등의 방법을 사용할 수 있다.In the case of a lithium ion battery negative electrode (hereinafter sometimes referred to as negative electrode), the slurry of the present invention is applied on the metal foil to a thickness of 1 to 100 mu m. As the metal foil, copper foil is generally used. Screen printing, roll coating, slit coating, and the like can be used for coating.
결합제로서 폴리이미드 전구체를 사용하는 경우, 도포 후, 100 내지 500℃에서 1분간 내지 24시간 열 처리함으로써, 폴리이미드 전구체를 폴리이미드로 변환하여, 신뢰성이 있는 부극을 얻을 수 있다. 바람직하게는 200℃ 이상 내지 450℃에서 이하의 온도에서 30분간 내지 이상 20시간 이하 처리하는 것이다. 또한, 수분의 혼입을 억제하기 위하여 질소 가스 등의 불활성 가스 중, 혹은 진공 중에서 가열하는 것이 바람직하다. 또한, 결합제로서 폴리이미드를 사용하는 경우, 도포 후, 80℃ 내지 500℃에서 1분간 내지 24시간 가열 처리함으로써, 용매를 제거하는 것이 바람직하다. 특별히 이미드화할 필요가 없기 때문에, 100℃ 내지 250℃에서 10분간 내지 24시간 처리하는 것이 보다 바람직하다. 어느 경우에서든 또한, 수분의 혼입을 억제하기 위하여, 질소 가스 등의 불활성 가스 중 또는 진공 중에서 가열하는 것이 바람직하다.When a polyimide precursor is used as the binder, the polyimide precursor is converted into polyimide by heat treatment at 100 to 500 ° C for 1 minute to 24 hours after application, thereby obtaining a reliable negative electrode. Preferably at a temperature of 200 ° C or more to 450 ° C or less for 30 minutes to 20 hours or less. Further, in order to suppress the incorporation of moisture, it is preferable to heat in an inert gas such as nitrogen gas or in a vacuum. When polyimide is used as the binder, it is preferable to remove the solvent by applying a heat treatment at 80 to 500 캜 for 1 minute to 24 hours after application. It is more preferable to carry out the treatment at 100 ° C to 250 ° C for 10 minutes to 24 hours since there is no need for imidization. In any case, it is preferable to heat in an inert gas such as nitrogen gas or in a vacuum to suppress the incorporation of moisture.
결합제에 저온 분해 수지를 포함하는 경우, 열 처리에 의해 저온 분해 수지를 분해함으로써, 기공이 내부에 있는 부극을 얻을 수 있다. 이 경우, 저온 분해 수지의 분해 온도보다 높고, 결합제의 분해 온도보다 낮은 온도에서 열 처리하는 것이 바람직하다. 이러한 온도 범위로서는 300℃ 내지 450℃에서 30분간 내지 20시간 처리하는 것이 바람직하다. 또한, 이러한 열 분해성의 수지로서는 폴리에틸렌글리콜, 폴리프로필렌글리콜 등이 있다.When the binder contains a low-temperature decomposition resin, the low-temperature decomposition resin is decomposed by heat treatment to obtain a negative electrode having pores therein. In this case, it is preferable to perform the heat treatment at a temperature higher than the decomposition temperature of the low-temperature decomposition resin and lower than the decomposition temperature of the binder. Such a temperature range is preferably treated at 300 캜 to 450 캜 for 30 minutes to 20 hours. Examples of such thermally decomposable resins include polyethylene glycol, polypropylene glycol, and the like.
리튬 전지 정극(이하, 정극이라고 칭하는 경우가 있음), 전기 2중층 캐패시터 정부극의 경우, 본 발명의 슬러리를 금속박 위에 1 내지 500㎛의 두께로 도포한다. 금속박으로서는, 알루미늄박, 니켈박, 티타늄박, 구리박 등을 들 수 있고, 알루미늄박이 일반적으로 사용된다. 도포 방법, 열 처리 방법은 리튬 전지 부극과 마찬가지이다.In the case of a lithium battery positive electrode (hereinafter sometimes referred to as a positive electrode) and an electric double layer capacitor negative electrode, the slurry of the present invention is applied on the metal foil to a thickness of 1 to 500 μm. Examples of the metal foil include aluminum foil, nickel foil, titanium foil and copper foil, and aluminum foil is generally used. The application method and the heat treatment method are the same as those of the lithium battery negative electrode.
이어서, 본 발명의 정극 및 부극을 사용한 리튬 이온 전지, 전기 2중층 캐패시터에 대하여 설명한다.Next, a lithium ion battery and an electric double layer capacitor using the positive electrode and the negative electrode of the present invention will be described.
본 발명의 정극과 부극에 대하여, 세퍼레이터를 개재시켜 복수 적층시킨 것을, 전해액과 함께 금속 케이스 등의 외장재에 넣어, 밀봉함으로써, 2차 전지나 전기 2중층 캐패시터를 얻을 수 있다.A secondary battery or an electric double-layer capacitor can be obtained by putting a plurality of positive electrodes and negative electrodes of the present invention, which are laminated with a separator interposed therebetween, together with an electrolyte in a casing such as a metal case and sealing them.
세퍼레이터의 예로서는, 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀이나, 셀룰로오스, 폴리페닐렌술피드, 아라미드, 폴리이미드 등의 미다공 필름이나 부직포 등을 들 수 있다.Examples of the separator include polyolefins such as polyethylene and polypropylene, and microporous films and nonwoven fabrics such as cellulose, polyphenylene sulfide, aramid and polyimide.
내열성을 올리기 위하여, 세퍼레이터의 표면에 세라믹 등의 코팅을 해도 된다.In order to increase heat resistance, the surface of the separator may be coated with ceramics or the like.
전해액에 사용하는 용매는, 전지의 전기 화학적 반응에 관여하는 이온이 이동할 수 있는 매질의 역할을 한다. 바람직한 용매로서는, 카르보네이트계, 에스테르계, 에테르계, 케톤계, 알코올계, 비양자성 용매를 들 수 있다. 상기 카르보네이트계 용매로서는, 디메틸카르보네이트(DMC), 디에틸카르보네이트(DEC), 디프로필카르보네이트(DPC), 메틸프로필카르보네이트(MPC), 에틸프로필카르보네이트(EPC), 메틸에틸카르보네이트(MEC), 에틸메틸카르보네이트(EMC), 에틸렌카르보네이트(EC), 프로필렌카르보네이트(PC), 부틸렌카르보네이트(BC) 등을 들 수 있다. 상기 에스테르계 용매로서는, 메틸아세테이트, 에틸아세테이트, n-프로필아세테이트, 메틸프로피온산염, 에틸프로피온산염, γ-부티로락톤, 데카노라이드, 발레로락톤, 메발로노락톤, 카프로락톤 등을 들 수 있다. 상기 에테르계 용매로서는, 디부틸에테르, 테트라글라임, 디글라임, 디메톡시에탄, 2-메틸테트라히드로푸란, 테트라히드로푸란 등을 들 수 있다. 상기 케톤계 용매로서는, 시클로헥사논 등을 들 수 있다. 상기 알코올계 용매로서는, 에틸알코올, 이소프로필알코올 등을 들 수 있다. 상기 비양자성 용매로서는, 톨릴류, 디메틸포름아미드 등의 아미드류, 1,3-디옥솔란 등의 디옥솔란류, 술포란류 등을 들 수 있다. 이들을 2종 이상 사용해도 되고, 함유량비는 목적으로 하는 전지의 성능에 따라 적절히 선택할 수 있다. 예를 들어, 상기 카르보네이트계 용매의 경우, 환상 카르보네이트와 쇄상 카르보네이트를 1:1 내지 1:9의 부피비로 조합하여 사용하는 것이 바람직하고, 전해액의 성능을 향상시킬 수 있다.The solvent used for the electrolytic solution serves as a medium through which ions involved in the electrochemical reaction of the battery can move. Preferred examples of the solvent include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, and aprotic solvent. Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate ), Methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone, decanol, valerolactone, mevalonolactone and caprolactone. have. Examples of the ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like. Examples of the ketone-based solvent include cyclohexanone and the like. Examples of the alcohol-based solvent include ethyl alcohol, isopropyl alcohol and the like. Examples of the aprotic solvent include amides such as tolyl and dimethylformamide, dioxolanes such as 1,3-dioxolane, and sulfolanes. Two or more of these may be used, and the content ratio can be appropriately selected according to the performance of the intended battery. For example, in the case of the above-mentioned carbonate-based solvent, it is preferable to use cyclic carbonate and chain carbonate in a volume ratio of 1: 1 to 1: 9, thereby improving the performance of the electrolytic solution.
전해액에 사용하는 전해질의 예로서는, 헥사플루오로인산리튬, 붕불화리튬, 과염소산리튬 등의 리튬염, 테트라에틸암모늄테트라플루오로보레이트, 트리에틸메틸암모늄테트라플루오로보레이트 등의 암모늄염 등을 들 수 있다.Examples of the electrolyte used in the electrolytic solution include lithium salts such as lithium hexafluorophosphate, lithium borofluoride and lithium perchlorate, and ammonium salts such as tetraethylammonium tetrafluoroborate and triethylmethylammonium tetrafluoroborate.
본 발명의 수지, 수지 조성물, 슬러리에 의해 형성한 피막, 적층체는, 반도체 패키지나 다층 배선판 등의 전자 부품에 사용할 수 있다. 구체적으로는, 반도체의 패시베이션막, 반도체 소자의 표면 보호막, 층간 절연막, 고밀도 실장용 다층 배선의 층간 절연막, 유기 전계 발광 소자의 절연층 등의 용도에 적합하게 사용되지만, 이것에 제한되지 않고, 다양한 구조를 취할 수 있다. 또한, 수지 조성물이 도전성 필러를 함유하는 경우에는, 배선 재료로서 사용할 수도 있다.The resin, the resin composition, the film and the laminate formed by the slurry of the present invention can be used for electronic parts such as a semiconductor package and a multilayer wiring board. Specifically, it is suitably used for a passivation film of a semiconductor, a surface protective film of a semiconductor element, an interlayer insulating film, an interlayer insulating film of a multilayer interconnection for high density mounting, an insulating layer of an organic electroluminescent element, Structure can be taken. When the resin composition contains an electrically conductive filler, it may be used as a wiring material.
실시예Example
이하, 실시예 등을 예시하여 본 발명을 설명하지만, 본 발명은 이들 예에 의하여 한정되는 것은 아니다. 또한, 실시예 중의 조성물의 평가는 이하의 방법에 의해 행했다.Hereinafter, the present invention will be described by way of examples and the like, but the present invention is not limited to these examples. The compositions in Examples were evaluated by the following methods.
1) 조성물의 막 두께의 측정 방법1) Method of measuring film thickness of composition
다이닛본 스크린 세이조(주)제 람다에이스 STM-602를 사용하여, 수지막, 가열 경화 후의 피막 모두, 굴절률을 1.629로 하여 측정했다.Using a Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd., the resin film and the film after heat curing were measured with a refractive index of 1.629.
2) 조성물의 기계 특성(강도(㎫), 탄성률(㎬), 신도(%))의 측정 방법2) Method of measuring the mechanical properties (strength (MPa), elastic modulus (㎬), elongation (%)) of the composition
조성물 용액을 8인치의 실리콘 웨이퍼 위에 회전 도포하고, 계속해서, 120℃의 핫 플레이트(도쿄 일렉트론(주)제의 도포 현상 장치 Act-8 사용)로 3분간 베이크하여, 수지막을 얻었다.The composition solution was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes using a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) to obtain a resin film.
이 수지막을 이너트 오븐 CLH-21CD-S(고요 서모 시스템(주)제)를 사용하여, 산소 농도 20ppm 이하에서 5℃/분으로 200℃까지 승온하고, 200℃에서 1시간 가열 처리를 행한 후, 5℃/min으로 50℃까지 냉각했다. 계속해서 불산에 1 내지 4분간 침지하여 막을 기판으로부터 박리하고, 풍건하여 가열 처리 후의 피막을 얻었다. 회전 도포 시의 회전수는 가열 처리 후의 수지막 두께가 10㎛가 되도록 조정했다.The resin film was heated to 200 ° C at an oxygen concentration of 20 ppm or less at 5 ° C / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. Subsequently, the film was immersed in hydrofluoric acid for 1 to 4 minutes to peel off the film from the substrate and air-dried to obtain a film after heat treatment. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.
가열 처리 후의 피막에 대하여, 폭 1㎝, 길이 약 9㎝의 직사각형으로 커트한 것을 측정용 시료로 했다. 측정에는 "텐실론"(RTM-100; 오리엔테크제)을 사용하여, 측정 결과로부터 상위 5점의 평균값을 구했다.The coating film after the heat treatment was cut into a rectangular shape having a width of 1 cm and a length of about 9 cm. The average value of the top five points was obtained from the measurement results using "Tensilon" (RTM-100; Orientech).
3) 조성물의 열선팽창 계수(CTE)의 측정 방법3) Method of measuring the thermal expansion coefficient (CTE) of the composition
조성물 용액을 8인치의 실리콘 웨이퍼 위에 회전 도포하고, 계속해서, 120℃의 핫 플레이트(도쿄 일렉트론(주)제의 도포 현상 장치 Act-8 사용)로 3분간 베이크하여, 수지막을 얻었다.The composition solution was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes using a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) to obtain a resin film.
이 수지막을 이너트 오븐 CLH-21CD-S(고요 서모 시스템(주)제)를 사용하여, 산소 농도 20ppm 이하에서 5℃/분으로 200℃까지 승온하고, 200℃에서 1시간 가열 처리를 행한 후, 5℃/min으로 50℃까지 냉각했다. 계속해서 불산에 1 내지 4분간 침지하여 막을 기판으로부터 박리하고, 풍건하여 가열 처리 후의 피막을 얻었다. 회전 도포 시의 회전수는 가열 처리 후의 수지막 두께가 10㎛가 되도록 조정했다.The resin film was heated to 200 ° C at an oxygen concentration of 20 ppm or less at 5 ° C / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. Subsequently, the film was immersed in hydrofluoric acid for 1 to 4 minutes to peel off the film from the substrate and air-dried to obtain a film after heat treatment. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.
가열 처리 후의 피막에 대하여, 열 기계 분석 장치(에스아이아이·나노테크놀로지(주)제 EXSTAR6000 TMA/SS6000)를 사용하여, 질소 기류 하에서 측정을 행했다. 승온 방법은, 이하의 조건에서 행했다. 제1 단계에서 승온 레이트 5℃/min으로 200℃까지 승온하여 시료의 흡착수를 제거하고, 제2 단계에서 강온 레이트 5℃/min으로 실온까지 공랭했다. 제3 단계에서, 승온 레이트 5℃/min으로 본 측정을 행하여, 50℃ 내지 200℃의 열선팽창 계수의 평균값을 구했다.The film after the heat treatment was subjected to measurement under a nitrogen stream using a thermomechanical analyzer (EXSTAR6000 TMA / SS6000, manufactured by SII Co., Ltd., Nanotechnology Co., Ltd.). The temperature rising method was performed under the following conditions. In the first step, the temperature of the sample was raised to 200 ° C at a heating rate of 5 ° C / min to remove the adsorbed water of the sample, and then cooled to room temperature at a cooling rate of 5 ° C / min in the second step. In the third step, this measurement was carried out at a heating rate of 5 캜 / min to obtain an average value of the thermal expansion coefficient at 50 캜 to 200 캜.
4) 구리와의 접착성4) Adhesion to copper
8인치의 실리콘 웨이퍼 위에 500㎚ 두께로 형성된 구리 기판을 준비했다. 이 기판 위에 조성물을 회전 도포하고, 계속해서, 120℃의 핫 플레이트(도쿄 일렉트론(주)제의 도포 현상 장치 Act-8 사용)로 3분간 베이크하여, 수지막을 얻었다.A copper substrate formed to a thickness of 500 nm on an 8-inch silicon wafer was prepared. The composition was spin-coated on the substrate, and then baked for 3 minutes with a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) to obtain a resin film.
이 수지막을 이너트 오븐 CLH-21CD-S(고요 서모 시스템(주)제)를 사용하여, 산소 농도 20ppm 이하에서 5℃/분으로 200℃까지 승온하고, 200℃에서 1시간 가열 처리를 행한 후, 5℃/min으로 50℃까지 냉각했다. 회전 도포 시의 회전수는 가열 처리 후의 수지막 두께가 10㎛가 되도록 조정했다.The resin film was heated to 200 ° C at an oxygen concentration of 20 ppm or less at 5 ° C / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.
가열 처리 후의 피막에 대하여, 121℃, 2기압의 포화 조건에서 400시간 가열 가습 처리한 후에, 2㎜ 간격으로 10행 10열의 바둑판눈 형상의 절입을 넣고, 셀로판테이프(등록 상표)에 의한 박리에 의해 100칸 중 몇칸 남았는지로 구리와의 접착성의 평가를 행했다.The heat-treated film was subjected to heating and humidifying treatment at 121 캜 under a saturated condition of 2 atmospheres for 400 hours, followed by inserting a checkerboard-shaped indentation of 10 rows and 10 columns at intervals of 2 mm and peeling off with a cellophane tape (registered trademark) The adhesion of copper to copper was evaluated according to how many of the 100 squares remained.
5) 실리콘의 접착성5) Adhesion of silicone
8인치의 실리콘 웨이퍼 위에 조성물을 회전 도포하고, 계속해서, 120℃의 핫 플레이트(도쿄 일렉트론(주)제의 도포 현상 장치 Act-8 사용)로 3분간 베이크하여, 수지막을 얻었다.The composition was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes with a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) to obtain a resin film.
이 수지막을 이너트 오븐 CLH-21CD-S(고요 서모 시스템(주)제)를 사용하여, 산소 농도 20ppm 이하에서 5℃/분으로 200℃까지 승온하고, 200℃에서 1시간 가열 처리를 행한 후, 5℃/min으로 50℃까지 냉각했다. 회전 도포 시의 회전수는 가열 처리 후의 수지막 두께가 10㎛가 되도록 조정했다.The resin film was heated to 200 ° C at an oxygen concentration of 20 ppm or less at 5 ° C / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.
가열 처리 후의 피막에 대하여, 121℃, 2기압의 포화 조건에서 400시간 가열 가습 처리한 후에, 2㎜ 간격으로 10행 10열의 바둑판눈 형상의 절입을 넣고, 셀로판테이프(등록 상표)에 의한 박리에 의해 100칸 중 몇칸 남았는지로 실리콘의 접착성의 평가를 행했다.The heat-treated film was subjected to heating and humidifying treatment at 121 캜 under a saturated condition of 2 atmospheres for 400 hours, followed by inserting a checkerboard-shaped indentation of 10 rows and 10 columns at intervals of 2 mm and peeling off with a cellophane tape (registered trademark) The adhesion of silicon was evaluated based on how many of the 100 squares remained.
6) 용량 유지율6) Capacity retention rate
본 발명의 조성물을 사용하여 이하의 수순에 따라 행했다.Using the composition of the present invention, the following procedure was followed.
a) 부극의 제작a) Production of negative electrode
합성예 1에서 얻은 부극 활물질 80중량부와, 고형분 농도 20%의 조성물 75중량부와, 도전 보조제로서 아세틸렌 블랙 5중량부를, 적량의 NMP에 용해시켜 교반한 후, 슬러리상의 페이스트를 얻었다. 얻어진 페이스트를, 전해 구리박 위에 닥터 블레이드를 사용하여 도포하고, 110℃에서 30분간 건조시키고, 롤 프레스기에 의해 프레스하여 전극으로 했다. 또한, 이 전극의 도포부를 직경 16㎜의 원형으로 펀칭하고, 200℃, 24시간의 진공 건조를 행하여, 부극을 제작했다.80 parts by weight of the negative electrode active material obtained in Synthesis Example 1, 75 parts by weight of a composition having a solid concentration of 20% and 5 parts by weight of acetylene black as a conductive auxiliary agent were dissolved in an appropriate amount of NMP and stirred to obtain a slurry-like paste. The obtained paste was applied on the electrolytic copper foil using a doctor blade, dried at 110 DEG C for 30 minutes, and pressed by a roll press machine to form an electrode. Further, the coated portion of the electrode was punched into a circle having a diameter of 16 mm, and vacuum drying was performed at 200 캜 for 24 hours to produce a negative electrode.
b) 전극 특성 평가b) Evaluation of electrode characteristics
충방전 특성을 측정하는 데 있어서는, HS 셀(호센(주)제)을 사용하여, 리튬 이온 전지의 조립은 질소 분위기 하에서 행했다. 셀 내에 제작한 부극을 직경 16㎜의 원형으로 펀칭한 것, 세퍼레이터가 되는 다공질 필름(호센(주)제)을 직경 24㎜로 펀칭한 것, 정극은, 코발트산리튬제의 활물질을 알루미늄박에 소성한 것(호센(주)제)을 직경 16㎜로 펀칭한 것을 순서대로 포개어, 전해액으로서 MIRET1(미쓰이 가가쿠(주)제) 1mL를 주입한 후 봉입하여, 리튬 이온 전지를 얻었다.In the measurement of the charge-discharge characteristics, the assembly of the lithium ion battery was performed in a nitrogen atmosphere using an HS cell (manufactured by Hoso Corporation). A negative electrode prepared in the cell was punched in a circular shape having a diameter of 16 mm and a porous film (manufactured by Hoso Corporation) serving as a separator was punched to a diameter of 24 mm. The positive electrode was obtained by mixing an active material made of lithium cobalt oxide with an aluminum foil (Manufactured by Hosene Corporation) was poured in a diameter of 16 mm, and 1 mL of MIRET1 (manufactured by Mitsui Chemicals, Inc.) was injected as an electrolytic solution and sealed to obtain a lithium ion battery.
상기한 바와 같이 하여 제작한 리튬 이온 전지를, 6㎃의 정전류로 전지 전압이 4.2V로 될 때까지 충전하고, 추가로 4.2V의 정전압으로 충전 개시부터 총 2시간 30분에 도달할 때까지 충전시킨 후, 30분간 휴지시키고, 6㎃의 정전류로 전지 전압이 2.7V가 될 때까지 방전시키고, 1사이클째의 충방전을 행했다. 또한, 이 후 19회 마찬가지의 조건에서 충방전을 반복하고, 합계 20사이클에 대하여, 각 사이클의 충전 용량 및 방전 용량을 측정했다.The lithium ion battery prepared as described above was charged at a constant current of 6 mA until the battery voltage reached 4.2 V and was further charged to a constant voltage of 4.2 V until reaching a total of 2 hours and 30 minutes Thereafter, the battery was stopped for 30 minutes, discharged at a constant current of 6 mA until the battery voltage reached 2.7 V, and charged and discharged in the first cycle. Charging and discharging were repeated 19 times under the same conditions, and the charging capacity and discharging capacity of each cycle were measured for a total of 20 cycles.
이하의 식에 따라, 용량 유지율을 산출했다.The capacity retention rate was calculated according to the following equation.
용량 유지율(%)=(20사이클째의 방전 용량/1사이클째의 방전 용량)×100Capacity Retention Rate (%) = (Discharge Capacity at the 20th Cycle / Discharge Capacity at the First Cycle) × 100
실시예 1Example 1
건조 질소 기류 하에서, 아민 성분으로서 o-톨리딘디이소시아네이트 10.6g(0.04몰:40몰%), 2,4-톨릴렌디이소시아네이트 3.48g(0.02몰:20몰%), 및 4,4'-디페닐메탄디이소시아네이트 10.0g(0.04몰:40몰%)을 N-메틸-2-피롤리돈(NMP) 120g에 용해시켰다. 여기에 산 성분으로서 무수 트리멜리트산 19.2g(0.1몰:100몰%)을 NMP 17.9g과 함께 첨가하고, 120℃에서 2시간, 140℃에서 2시간 반응시켜 수지 농도 20%의 조성물 1을 얻었다.(0.04 mol: 40 mol%) of o-tolylene diisocyanate, 3.48 g (0.02 mol: 20 mol%) of 2,4-tolylene diisocyanate as an amine component, and 4,4'-diphenyl 10.0 g (0.04 mol: 40 mol%) of methane diisocyanate was dissolved in 120 g of N-methyl-2-pyrrolidone (NMP). 19.9 g (0.1 mol: 100 mol%) of trimellitic anhydride as an acid component was added together with 17.9 g of NMP, followed by reaction at 120 ° C for 2 hours and at 140 ° C for 2 hours to obtain a composition 1 having a resin concentration of 20% .
실시예 2 내지 9, 14, 비교예 1 및 2Examples 2 to 9, 14, Comparative Examples 1 and 2
표 1에 나타낸 아민 성분, 산 성분을 사용하여 실시예 1과 마찬가지의 방법으로 수지 농도 20%의 조성물 2 내지 9 및 14 내지 16을 얻었다.Compositions 2 to 9 and 14 to 16 having a resin concentration of 20% were obtained in the same manner as in Example 1, using the amine component and the acid component shown in Table 1.
실시예 10Example 10
건조 질소 기류 하에서, 아민 성분으로서 o-톨리딘디이소시아네이트 18.5g(0.07몰:70몰%), 2,4-톨릴렌디이소시아네이트 5.22g(0.03몰:30몰%)을 NMP 120g에 용해시켰다. 여기에 말단 밀봉제로서 2-부타논옥심 0.871g(0.01몰:10몰%)을 NMP 10g과 함께 첨가하고, 70℃에서 2시간 반응시키고, 이어서 산 성분으로서 무수 트리멜리트산 18.3g(0.095몰:95몰%)을 NMP 8.12g과 함께 첨가하고, 120℃에서 2시간, 140℃에서 2시간 반응시켜 수지 농도 20%의 조성물 10을 얻었다.18.5 g (0.07 mol: 70 mol%) of o-tolylidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate as an amine component were dissolved in 120 g of NMP under a dry nitrogen stream. Then, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as a terminal sealing agent was added together with 10 g of NMP, and the reaction was carried out at 70 DEG C for 2 hours. Then, 18.3 g (0.095 mol) of anhydrous trimellitic acid : 95 mol%) was added together with 8.12 g of NMP, and the mixture was reacted at 120 占 폚 for 2 hours and at 140 占 폚 for 2 hours to obtain a composition 10 having a resin concentration of 20%.
실시예 11Example 11
표 1에 나타낸 아민 성분, 산 성분 및 말단 밀봉재를 사용하여 실시예 10과 마찬가지의 방법으로 수지 농도 20%의 조성물 11을 얻었다.Composition 11 having a resin concentration of 20% was obtained in the same manner as in Example 10 by using the amine component, the acid component and the terminal sealing material shown in Table 1.
실시예 12Example 12
건조 질소 기류 하에서, 아민 성분으로서 o-톨리딘디이소시아네이트 18.5g(0.07몰:70몰%), 2,4-톨릴렌디이소시아네이트 5.22g(0.03몰:30몰%)을 NMP 120g에 용해시켰다. 여기에 말단 밀봉제로서 2-부타논옥심 0.871g(0.01몰:10몰%)을 NMP 10g과 함께 첨가하고, 70℃에서 2시간 반응시키고, 이어서 산 성분으로서 무수 트리멜리트산 18.3g(0.095몰:95몰%)을 NMP 15.0g과 함께 첨가하고, 120℃에서 2시간, 140℃에서 2시간 반응시켰다. 그 후 액온을 60℃로 강온하고, 3-아미노프로필트리메톡시실란 1.73g(수지 100중량에 대하여 5중량)을 첨가하고 이어서 60℃에서 3시간 교반하여, 수지와 실란 화합물의 합계가 20%의 농도가 되는 조성물 12를 얻었다.18.5 g (0.07 mol: 70 mol%) of o-tolylidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate as an amine component were dissolved in 120 g of NMP under a dry nitrogen stream. Then, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as a terminal sealing agent was added together with 10 g of NMP, and the reaction was carried out at 70 DEG C for 2 hours. Then, 18.3 g (0.095 mol) of anhydrous trimellitic acid : 95 mol%) was added together with 15.0 g of NMP, and the mixture was reacted at 120 캜 for 2 hours and at 140 캜 for 2 hours. Thereafter, the temperature of the solution was lowered to 60 캜, 1.73 g of 3-aminopropyltrimethoxysilane (5 weight% based on 100 weight of the resin) was added and the mixture was stirred at 60 캜 for 3 hours to obtain a resin- ≪ / RTI >
실시예 13Example 13
표 1에 나타낸 아민 성분, 산 성분, 말단 밀봉재 및 실란 화합물을 사용하여 실시예 12와 마찬가지의 방법으로 수지와 실란 화합물의 합계가 20%의 농도가 되는 조성물 13을 얻었다.Using the amine component, the acid component, the terminal sealing material and the silane compound shown in Table 1, a composition 13 in which the sum of the resin and the silane compound was 20% was obtained in the same manner as in Example 12. [
비교예 3Comparative Example 3
건조 질소 기류 하에서, 아민 성분으로서 4,4'-디아미노디페닐에테르 20.0g(0.1몰:100몰%)을 NMP 150g에 용해시켰다. 여기에 산 성분으로서 무수 피로멜리트산 20.7g(0.095몰:95몰%)을 NMP 12.9g과 함께 첨가하고, 40℃에서 6시간 반응시켜 수지 농도 20%의 조성물 17을 얻었다.20.0 g (0.1 mol: 100 mol%) of 4,4'-diaminodiphenyl ether as an amine component was dissolved in 150 g of NMP under a dry nitrogen flow. 20.7 g (0.095 mol: 95 mol%) of anhydrous pyromellitic acid as an acid component was added together with 12.9 g of NMP and reacted at 40 DEG C for 6 hours to obtain a composition 17 having a resin concentration of 20%.
비교예 4Comparative Example 4
건조 질소 기류 하에서, 아민 성분으로서 4,4'-디아미노디페닐술폰 24.8g(0.1몰:100몰%)을 NMP 180g에 용해시켰다. 여기에 산 성분으로서 옥시디프탈산 이무수물 30.4g(0.98몰:98몰%)을 NMP 26.4g과 함께 첨가하고, 200℃에서 6시간 반응시켜 수지 농도 20%의 조성물 18을 얻었다.24.8 g (0.1 mol: 100 mol%) of 4,4'-diaminodiphenyl sulfone as an amine component was dissolved in 180 g of NMP under a dry nitrogen flow. Thereto was added 30.4 g (0.98 mol: 98 mol%) of oxydiphthalic dianhydride as an acid component together with 26.4 g of NMP and reacted at 200 DEG C for 6 hours to obtain a composition 18 having a resin concentration of 20%.
합성예 1 부극 활물질의 합성Synthesis Example 1 Synthesis of negative electrode active material
메디안 직경 10㎛의 천연 흑연 50g(후지 흑연(주)제, CBF1)과 나노 실리콘 분말 60g(알드리치사제)과, 카본 블랙 10g(미쯔비시 가가꾸(주)제, 3050)을 혼합하고, 볼 밀 중 600회전으로 12시간 잘 분산시키고, 그 후, 80℃에서 12시간 진공 건조하여 Si-C계의 부극 활물질을 얻었다. 이 메디안 직경은 10㎛였다.(CBF1 manufactured by Fuji Graphite Co., Ltd.), 60 g of nano silicon powder (manufactured by Aldrich) and 10 g of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., 3050) having a median diameter of 10 탆 were mixed, Well dispersion at 600 rpm for 12 hours and then vacuum drying at 80 캜 for 12 hours to obtain a Si-C negative electrode active material. The median diameter was 10 占 퐉.
조성물 1 내지 18의 조성 및 평가 결과에 대하여, 실시예 1 내지 14, 비교예 1 내지 4로서 표 1에 나타낸다.The composition and evaluation results of the compositions 1 to 18 are shown in Table 1 as Examples 1 to 14 and Comparative Examples 1 to 4.
Claims (18)
(일반식 (1) 중 R1은 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R2는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. R3은 수소 원자 또는 탄소수 1 내지 10의 유기기를 나타낸다. m1은 1 또는 2의 정수이다.)
(일반식 (2) 중 R4는 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R5는 탄소수 2 내지 50의 3가 또는 4가의 유기기를 나타낸다. m2는 0 또는 1의 정수, c1은 0 또는 1의 정수이며, m2=0일 때 c1=1, m2=1일 때 c1=0이다.)
(일반식 (3) 중 R6 및 R7은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b1 및 b2는 각각 독립적으로 0 내지 3의 정수이다.)
(일반식 (4) 중 R8은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b3은 0 내지 4의 정수이다.)A resin having a structural unit represented by the following general formula (1) and / or a structural unit represented by the following general formula (2), wherein R 1 and R 4 contained in the resin each independently represent, A resin comprising a structure represented by the formula (3) and a structure represented by the following formula (4).
(In the general formula (1), R 1 represents a divalent organic group having 2 to 50 carbon atoms, R 2 represents a tricyclic or tetravalent organic group having 2 to 50 carbon atoms, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms M < 1 > is an integer of 1 or 2.)
(Formula (2): R 4 represents a divalent organic group having 2 to 50. R 5 is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M 2 is an integer, c 1 0 or 1, Is an integer of 0 or 1, c 1 = 1 when m 2 = 0, and c 1 = 0 when m 2 = 1.)
(In the general formula (3), R 6 and R 7 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b 1 and b 2 each independently represent an integer of 0 to 3.)
(In the general formula (4), R 8 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b 3 is an integer of 0 to 4)
(일반식 (5) 내지 (6) 중 R9 및 R10은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b4 및 b5는 0 내지 4의 정수이다.)4. The compound according to any one of claims 1 to 3, wherein R 2 and R 5 each independently represent a structure represented by the following general formula (5) or (6) Suzy.
(In the formulas (5) to (6), R 9 and R 10 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b 4 and b 5 are integers of 0 to 4)
(일반식 (7) 중 R11은 탄소수 2 내지 50의 2가의 유기기를 나타낸다. R12는 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 3의 1가의 유기기를 나타낸다. b6은 0 내지 4의 정수이다.)The resin according to any one of claims 1 to 4, further comprising 5 to 30 mol% of a structural unit represented by the following general formula (7).
(7), R 11 represents a divalent organic group having 2 to 50 carbon atoms, R 12 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b 6 is an integer of 0 to 4 .)
(일반식 (8) 중 R13 내지 R16은 각각 독립적으로 할로겐 원자 또는 탄소수 1 내지 5의 1가의 유기기를 나타낸다.)6. The resin according to any one of claims 1 to 5, wherein the terminal structure has a structure represented by the following general formula (8).
(In the general formula (8), R 13 to R 16 each independently represent a halogen atom or a monovalent organic group having 1 to 5 carbon atoms.)
(상기 일반식 (9) 중 R17은 탄소수 1 내지 4의 알콕실기, R18은 탄소수 1 내지 4의 알콕실기 또는 알킬기, R19는 탄소수 1 내지 4의 2가의 유기기, Z는 이소시아네이트기와 반응성이 있는 관능기를 나타낸다.)The resin solution according to claim 8, further comprising c) a silane compound represented by the following general formula (9).
(Wherein R 17 is an alkoxyl group having 1 to 4 carbon atoms, R 18 is an alkoxyl group or alkyl group having 1 to 4 carbon atoms, R 19 is a divalent organic group having 1 to 4 carbon atoms, Z is a reactive group having an isocyanate group Represents a functional group having a hydroxyl group.
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