CN113024773A - Modified acrylate resin, preparation method thereof, solder resist ink and printed circuit board - Google Patents
Modified acrylate resin, preparation method thereof, solder resist ink and printed circuit board Download PDFInfo
- Publication number
- CN113024773A CN113024773A CN202010175045.8A CN202010175045A CN113024773A CN 113024773 A CN113024773 A CN 113024773A CN 202010175045 A CN202010175045 A CN 202010175045A CN 113024773 A CN113024773 A CN 113024773A
- Authority
- CN
- China
- Prior art keywords
- resin
- acrylate resin
- ink
- esterification catalyst
- modified acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 86
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 86
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000011241 protective layer Substances 0.000 claims abstract description 35
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 238000007641 inkjet printing Methods 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims description 55
- 230000032050 esterification Effects 0.000 claims description 54
- 238000005886 esterification reaction Methods 0.000 claims description 54
- -1 β -carboxyethyl Chemical group 0.000 claims description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 claims description 8
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 7
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 3
- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 claims description 3
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000012752 auxiliary agent Substances 0.000 abstract description 7
- 239000012776 electronic material Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical group 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 77
- 238000001723 curing Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000007639 printing Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OHPZDPGRPOVAJJ-UHFFFAOYSA-N C1C(C)O1.C=C.C(O)C(CC)(CO)CO Chemical compound C1C(C)O1.C=C.C(O)C(CC)(CO)CO OHPZDPGRPOVAJJ-UHFFFAOYSA-N 0.000 description 1
- GEXVUFWVPUWPJB-UHFFFAOYSA-N ClC1=CC=2SC3=CC=CC=C3S(C2C=C1)=O Chemical compound ClC1=CC=2SC3=CC=CC=C3S(C2C=C1)=O GEXVUFWVPUWPJB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- KDONFNVMZBKJTJ-UHFFFAOYSA-N diethoxyphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C KDONFNVMZBKJTJ-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention belongs to the technical field of electronic materials, and particularly relates to a modified acrylate resin, a preparation method thereof, solder mask ink and a printed circuit board. The invention takes the modified acrylate resin obtained by the ring-opening polymerization reaction of the long-chain end epoxy resin and the unsaturated carboxylic acid unit as the resin material, and then mixes the resin material with the acrylate or acrylic resin, the curing agent, the reactive diluent, the photoinitiator, the nano color paste and the auxiliary agent, so that the obtained solder-proof ink is environment-friendly, has low viscosity and meets the requirements of digital ink-jet printing. The invention can realize that the solder mask ink is printed on the printed circuit board in a large area and high precision in a digital ink-jet printing mode, and the protective layer formed by curing has good performance and meets the IPC industry standard.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a modified acrylate resin, a preparation method thereof, solder mask ink and a printed circuit board.
Background
The solder resist ink is a permanent protective coating printed on the surface of a circuit board with a circuit pattern in a large area, the coating selectively masks wires to prevent the pattern from being damaged, short circuit does not occur during solder resist, and the dosage of film forming substances is very large, and the solder resist ink has the characteristics of chemical resistance, solvent resistance, heat resistance, insulativity, moisture resistance, salt mist resistance, prevention of adhesion of soldering tin to an unnecessary part, prevention of pollution of copper to a soldering tin bath and the like.
The most used photosensitive solder mask ink in the current printed circuit board is solvent type ink, the VOC emission is high, the process application flow is complex, and the process flow is as follows: printing, prebaking, sticking film (film manufacturing), exposing, developing and thermocuring. A large amount of consumables such as half tone, film need be used to whole process, still can produce a large amount of waste water simultaneously, and each section technology all needs personnel to link up and operate, and degree of automation is lower. Along with the increasingly strict requirements on environmental protection and higher labor cost of the country, the requirement of the whole industry on automation is higher and higher, and the industry provides a new process for realizing the coating of the anti-welding coating by using ink-jet digital printing equipment. The process flow is as follows: printing, LED UV curing and thermosetting, the flow is obviously shortened, a large amount of personnel is not needed for connection operation, and the automation degree is high.
The ink-jet digital printing technology is a mature technology in other industries, and is gradually popularized in the PCB manufacturing industry in recent years, but the technology is mainly applied to PCB character printing, the requirement on precision is relatively low, and the precision is far from enough when the technology is used for PCB solder mask.
Disclosure of Invention
The invention aims to provide a modified acrylate resin, a preparation method thereof, solder mask ink and a printed circuit board, and aims to solve the technical problems that the traditional photosensitive solder mask ink is not suitable for digital ink-jet printing and the like.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of modified acrylate resin, which comprises the following steps:
the long-chain end epoxy resin and unsaturated unit carboxylic acid are subjected to ring-opening polymerization reaction to obtain the modified acrylate resin;
wherein the epoxy equivalent of the long-chain epoxy-terminated resin is 80-250 g/eq.
In a preferred embodiment of the present invention, the long-chain epoxy-terminated resin is at least one selected from the group consisting of bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, hydrogenated bisphenol a epoxy resin, triglycidyl p-aminophenol, and pentaerythritol tetraglycidyl ether.
In a preferred embodiment of the present invention, the unsaturated monocarboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and β -carboxyethyl (meth) acrylate.
In a preferred embodiment of the present invention, the ring-opening polymerization is carried out in a reaction system containing an unsaturated monomer diluent.
In a further preferred embodiment of the present invention, the ring-opening polymerization is carried out in a reaction system containing an unsaturated monomer diluent selected from at least one of monofunctional unsaturated monomers, difunctional unsaturated monomers and polyfunctional unsaturated monomers.
As a preferred technical scheme of the invention, the ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst.
In a further preferred embodiment of the present invention, the ring-opening polymerization reaction is performed under the catalysis of an esterification catalyst, and the esterification catalyst is at least one selected from a tertiary amine esterification catalyst, a quaternary ammonium salt esterification catalyst, and a phosphine esterification catalyst.
In a further preferred embodiment of the present invention, the ring-opening polymerization reaction is performed under the catalysis of an esterification catalyst, the esterification catalyst is at least one selected from a tertiary amine esterification catalyst, a quaternary ammonium salt esterification catalyst, and a phosphine esterification catalyst, and the tertiary amine esterification catalyst is at least one selected from triethylamine, N-dimethylbenzylamine, and N, N-dimethylaniline.
In a further preferred embodiment of the present invention, the ring-opening polymerization reaction is performed under the catalysis of an esterification catalyst, the esterification catalyst is at least one selected from a tertiary amine esterification catalyst, a quaternary ammonium salt esterification catalyst, and a phosphine esterification catalyst, and the quaternary ammonium salt esterification catalyst is at least one selected from trimethyl benzyl ammonium chloride, methyl triethyl ammonium chloride, and hexadecyl trimethyl ammonium bromide.
In a further preferred embodiment of the present invention, the ring-opening polymerization is carried out under the catalysis of an esterification catalyst selected from at least one of tertiary amine esterification catalysts, quaternary ammonium salt esterification catalysts, and phosphine esterification catalysts selected from at least one of triphenylphosphine, tributylphosphine, triethylphosphine, tri-o-toluylphosphine, tri-m-toluylphosphine, tri-p-toluylphosphine, and tri (p-methoxyphenyl) phosphine.
In a preferred embodiment of the present invention, a polymerization inhibitor is further added to the ring-opening polymerization reaction.
In a more preferred embodiment of the present invention, a polymerization inhibitor is further added to the ring-opening polymerization reaction, and the polymerization inhibitor is at least one selected from hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, and p-hydroxyanisole.
Correspondingly, the invention provides a modified acrylate resin which is prepared by the preparation method of the modified acrylate resin, the modified acrylate resin is in a liquid state, the epoxy equivalent is 200g/eq-500g/eq, and the viscosity is less than 20000 mPa.s.
The invention also provides solder mask ink, which comprises the following components in percentage by weight, based on the total weight of the solder mask ink as 100 percent:
as a preferable technical scheme of the invention, the viscosity of the solder mask ink is 5-10 mPa.s at 50 ℃, the surface tension is 20-34 mN/m, and the particle size is less than 500 nm.
In a preferred embodiment of the present invention, the multifunctional acrylate is at least one selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and caprolactone-modified dipentaerythritol hexaacrylate.
In a preferred embodiment of the present invention, the acrylic resin is selected from the group consisting of a trifunctional amino acrylate resin, a hexafunctional amino acrylate resin, and a hexafunctional urethane acrylate resin.
In a preferred embodiment of the present invention, the curing agent is at least one selected from the group consisting of diaminodiphenyl sulfone, 4' diaminodiphenylmethane, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, boron trifluoride-amine complex, cationic initiator, iodohexafluoroantimonate, (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluoroantimonate, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile), and blocked isocyanate.
In a preferred embodiment of the present invention, the reactive diluent is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, (2-ethyl-2-methyl-1, 3-dioxolanyl-4) acrylate, (2-isopropyl-2-methyl-1, 3-dioxolanyl-4) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl alicyclic epoxy resin, alicyclic epoxy acrylate, and alicyclic epoxy methacrylate.
As a preferable technical solution of the present invention, the photoinitiator is at least one selected from an acylphosphine oxide photoinitiator, a benzoin photoinitiator, an aminoalkyl benzophenone photoinitiator, a benzophenone, a thioxanthone photoinitiator, and an iron arene photoinitiator.
In another aspect, the present invention provides a printed circuit board, wherein a protective layer is disposed on the printed circuit board, and the protective layer is obtained by inkjet printing the solder mask ink on the printed circuit board and curing the printed circuit board.
The preparation method of the modified acrylic resin of the invention has the advantages that the long-chain end epoxy resin and unsaturated carboxylic acid unit are subjected to ring-opening polymerization reaction, the operation steps are simple and easy to implement, and the generated modified acrylic polyester has the following characteristics: firstly, the solder resist ink has ethynyl and other active groups, so that the solder resist ink can be printed on a printed circuit board for curing reaction after being prepared as one of the components of the solder resist ink, thereby forming a protective layer; secondly, the cured protective layer has heat resistance because of the cyclic structure; and thirdly, the viscosity is low and liquid, and the resin is used as a resin component in the solder resist ink, so that the viscosity of the prepared solder resist ink is low, and the requirement of ink-jet printing on the construction viscosity of the solder resist ink is met.
The solder mask ink provided by the invention takes the curable modified acrylate resin with a ring structure and low viscosity as a resin material, and is supplemented with polyfunctional acrylate and/or acrylic resin, a curing agent, an active diluent, a photoinitiator, nano color paste and an auxiliary agent, so that the solder mask ink also has the advantages of low viscosity, curing property and good heat resistance, is high-precision and environment-friendly liquid solder mask ink, and can meet the requirements of large-area and high-precision digital ink-jet printing on the solder mask ink.
The solder mask ink is printed on a printed circuit board by a PCB digital ink-jet printer and cured to obtain a protective layer. The test shows that the protective layer has good adhesive force, good solvent resistance, acid resistance, alkali resistance, soldering resistance and electroplating resistance, and meets the requirements of IPC standard.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In the description of the invention, an expression of a word in the singular should be understood to include the plural of the word, unless the context clearly dictates otherwise. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
In the description of the present invention, when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
In this specification, "lower" or "upper" is not an absolute concept, but may be a relative concept that can be explained by replacing "upper" or "lower", respectively, according to the viewpoint of the observer.
The embodiment of the invention provides a preparation method of modified acrylate resin, which comprises the following steps:
the long-chain epoxy resin and unsaturated carboxylic acid unit are subjected to ring-opening polymerization reaction to obtain modified acrylate resin; wherein the epoxy equivalent of the long-chain epoxy-terminated resin is 80g/eq-250 g/eq.
Epoxy equivalent (epoxide equivalent) is the mass gram (g) of an epoxy resin containing 1mol of epoxy groups, and is the most important index for identifying the properties of the epoxy resin. In contrast, the larger the epoxy equivalent, the less epoxy groups in the epoxy resin with the same mass, the longer the molecular chain and the higher the viscosity, and the epoxy resin is easy to be in a semi-solid state or even a solid state; the smaller the epoxy equivalent, the more epoxy groups in the epoxy resin of the same mass, the shorter the molecular chain, the lower the viscosity, and the liquid state is often observed. According to the invention, the long-chain epoxy-terminated resin with the epoxy equivalent of 80-250 g/eq is selected to perform ring-opening polymerization reaction with unsaturated carboxylic acid unit, so that on one hand, the viscosity of the long-chain epoxy-terminated resin is lower due to the smaller epoxy equivalent, and correspondingly, the viscosity of the generated modified acrylate resin is also lower. On the other hand, the long-chain end epoxy resin reacts with the unsaturated carboxylic acid unit to provide ethynyl and other active groups (such as hydroxyl, carboxyl, epoxy and the like) and a cyclic structure for the modified acrylate resin, so that the modified acrylate resin can be endowed with the properties of photocuring and thermocuring and also has heat resistance. In addition, the preparation method of the modified acrylate resin can obtain the modified acrylate resin through simple steps, and has the advantage of convenient implementation.
To ensure that the long chain end epoxy resin and the resulting modified acrylate resin are of lower viscosity while providing sufficient cyclic structure, in some embodiments, a long chain end epoxy resin having an epoxy equivalent weight of 110g/eq to 180g/eq is selected for reaction with the unsaturated monocarboxylic acid.
In some embodiments, the long-chain epoxy-terminated resin is selected from at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, hydrogenated bisphenol a epoxy resin, triglycidyl para-aminophenol, pentaerythritol tetraglycidyl ether, thereby providing the resulting modified acrylic resin with a cyclic structure and a plurality of reactive groups to facilitate photo-curing and thermal curing reactions.
In some embodiments, the unsaturated monocarboxylic acid is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, and beta-carboxyethyl (meth) acrylate. These unsaturated monocarboxylic acids may impart carboxyl groups to the structure of the resulting modified acrylate resin, thereby further enhancing its reactivity in the curing reaction.
In the actual preparation of the modified acrylic resin of the present invention, whether or not the monomer diluent is unsaturated may be determined according to the viscosity of the long-chain epoxy-terminated resin used. If the viscosity of the long-chain epoxy-terminated resin is low, no additional unsaturated monomer diluent is needed; if the viscosity of the long-chain epoxy-terminated resin is high, the unsaturated monomer diluent may be appropriately used before the ring-opening polymerization reaction is completed in order to avoid an excessively high viscosity of the synthesized modified acrylate resin (which should be < 20000 mPa.s).
Preferably, the unsaturated monomer is selected from at least one of a monofunctional unsaturated monomer, a difunctional unsaturated monomer, and a polyfunctional unsaturated monomer.
Further, the monofunctional unsaturated monomer may be selected from at least one of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acryloyloxyethoxy-2-hydroxypropyl phthalate, lauric acid (meth) acrylate, methoxylated polyethylene glycol (meth) acrylate, stearic acid (meth) acrylate, benzyl acrylate, isodecyl (meth) acrylate, ethoxylated hydroxyl (meth) acrylate, methoxylated polyethylene glycol (meth) acrylate, glycidyl methacrylate, isooctyl (meth) acrylate, stearic acid (meth) acrylate; the difunctional unsaturated monomer is selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, tripropylene glycol diacrylate, neopentyl glycol di (meth) acrylate, dioxane glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, 2-hydroxyethyl methacrylate phosphate, ethoxylated bisphenol A dimethacrylate, diethylene glycol (meth) acrylate; the polyfunctional unsaturated monomer (i.e., trifunctional or higher than trifunctional unsaturated monomer) is selected from trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethylene (propylene) oxide trimethylolpropane tri (meth) acrylate, propoxylated glycerol triacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
Preferably, the ring-opening polymerization reaction of the present invention is carried out under the catalysis of an esterification catalyst to reduce the activation energy of the reaction and accelerate the reaction rate. The esterification catalyst is at least one of tertiary amine esterification catalyst, quaternary ammonium salt esterification catalyst and phosphine esterification catalyst.
Further, the tertiary amine esterification catalyst is selected from triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline; the quaternary ammonium salt esterification catalyst is selected from trimethyl benzyl ammonium chloride, methyl triethyl ammonium chloride, and hexadecyl trimethyl ammonium bromide; the phosphine esterification catalyst is selected from triphenylphosphine, tributylphosphine, triethylphosphine, tri-o-toluyl phosphine, tri-m-toluyl phosphine, tri-p-phenyl-formyl phosphine and tri (p-methoxyphenyl) phosphine.
Preferably, a polymerization inhibitor is further added in the ring-opening polymerization reaction of the invention for preventing the unsaturated bond from self-polymerization. The polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone and p-hydroxyanisole.
In some embodiments, the temperature of the ring-opening polymerization reaction is set between 100 ℃ and 110 ℃ (inclusive) to facilitate the reaction rate of the ring-opening polymerization reaction; the time for the ring-opening polymerization reaction is based on the acid value measured in the actual reaction, and the reaction is stopped when the acid value AV < 1. Specifically, typical, but not limiting, ring-opening polymerization temperatures are 100 deg.C, 102 deg.C, 104 deg.C, 105 deg.C, 106 deg.C, 108 deg.C, 110 deg.C.
By optimizing the addition amount of each reactant in the ring-opening polymerization reaction, the reaction rate of the ring-opening polymerization reaction can be improved, and the production cost is saved. Therefore, it is further preferable that the mass ratio of the long-chain epoxy resin, the unsaturated monocarboxylic acid, the polymerization inhibitor, the catalyst and the unsaturated monomer diluent is controlled to (60-80): (15-35): (0.02-0.1): (0.1-0.5): (0-10).
The embodiment of the invention provides the modified acrylate resin prepared by the preparation method, wherein the modified acrylate resin is in a liquid state, the epoxy equivalent is 200g/eq-500g/eq, and the viscosity is less than 20000 mPa.s.
The modified acrylic polyester of the invention has the following characteristics: firstly, the solder resist ink has ethynyl and other active groups, so that the solder resist ink can be printed on a printed circuit board for curing reaction after being prepared as one of the components of the solder resist ink, thereby forming a protective layer; secondly, the cured protective layer has heat resistance because of the cyclic structure; and thirdly, the viscosity is low and liquid, and the resin is used as a resin component in the solder resist ink, so that the viscosity of the prepared solder resist ink is low, and the requirement of ink-jet printing on the construction viscosity of the solder resist ink is met.
The embodiment of the invention provides solder mask ink by taking the modified acrylate resin as a raw material, wherein the solder mask ink comprises the following components in percentage by weight, based on 100% of the total weight of the solder mask ink:
the solder mask ink provided by the invention takes the curable modified acrylate resin with a ring structure and low viscosity as a resin material, and is supplemented with polyfunctional acrylate and/or acrylic resin, a curing agent, an active diluent, a photoinitiator, nano color paste and an auxiliary agent, so that the solder mask ink also has the advantages of low viscosity, curing property and good heat resistance, is high-precision and environment-friendly liquid solder mask ink, and can meet the requirements of large-area and high-precision digital ink-jet printing on the solder mask ink.
The function of the modified acrylate resin in the solder mask ink of the present invention is as described above, and will not be described herein. If the addition amount of the modified acrylate resin is too large, the viscosity of the obtained solder mask ink is increased, and the problems of difficult ink jetting of a nozzle and unsmooth printing during ink jetting are easily caused; if the amount of the modified acrylate resin added is too small, the heat resistance and plating resistance of the solder resist ink after curing are reduced. Therefore, the weight percentage of the modified acrylate resin in the solder mask ink is controlled to be 10% -15% in the embodiment of the invention. Specifically, typical, but not limiting, weight percent amounts of the modified acrylate resin are: 10%, 11%, 12%, 13%, 14%, 15%.
The multifunctional acrylate and/or acrylic resin can improve the surface drying performance of the obtained solder resist ink during photocuring. In some embodiments, the multifunctional acrylate is selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate; the multifunctional acrylic resin is at least one selected from the group consisting of trifunctional amino acrylate resin, hexafunctional amino acrylate resin and hexafunctional urethane acrylate resin. The problem that the adhesive force is reduced easily because the shrinkage after photocuring is too large when the addition amount of the multifunctional acrylate and/or the acrylic resin is too large; when the amount is too small, the surface of the protective layer formed after photocuring is not well dried and the problem of sticking easily occurs, and therefore, in some embodiments, the weight percentage of the multifunctional acrylate and/or acrylic resin in the solder resist ink is controlled to be 5% to 10%. In particular, the multifunctional acrylates and/or acrylic resins as a whole are typically, but not exclusively, contained in the following percentages by weight: 5%, 6%, 7%, 8%, 9%, 10%.
The curing agent is a substance for promoting or controlling the curing reaction, and can enable the resin to have the photo-curing reaction and the thermal curing reaction by adding the curing agent, and has obvious influence on the heat resistance and the stability of the obtained solder resist ink. In some embodiments, the curing agent is selected from at least one of diaminodiphenyl sulfone, 4' diaminodiphenylmethane, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, boron trifluoride-amine complex, cationic initiator, iodohexafluoroantimonate, (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluoroantimonate, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile), blocked isocyanates. The addition amount of the curing agent is too much, so that the flexibility of a protective layer formed on the printed circuit board by the solder resist ink is easily reduced, and the problems of cracking and the like occur; if the amount of the curing agent added is too low, problems such as incomplete curing reaction, and a decrease in the hardness and thermal stability of the solder resist ink after forming a protective layer on a printed circuit board may occur. Therefore, the embodiment of the invention controls the weight percentage of the curing agent in the solder mask ink to be 10-20%. Specifically, typical, but not limiting, amounts of the curing agent are as follows: 10%, 12%, 14%, 16%, 18%, 20%.
The reactive diluent can participate in the curing reaction of the modified acrylate resin, becomes a part of the cross-linked network structure of a cured product, and can reduce the viscosity of the system. In some embodiments, the reactive diluent is selected from at least one of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, (2-ethyl-2-methyl-1, 3-dioxolanyl-4) acrylate, (2-isopropyl-2-methyl-1, 3-dioxolanyl-4) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl cycloaliphatic epoxy resin, cycloaliphatic epoxy acrylate, cycloaliphatic epoxy methacrylate. If the addition amount of the reactive diluent is too large, the curing reaction rate is easily reduced, and the reaction time is prolonged; if the amount of the reactive diluent added is too small, the viscosity of the solder resist ink obtained may be too high to be used for ink jet printing. Therefore, the weight percentage of the reactive diluent in the solder mask ink is controlled to be 45-55% in the embodiment of the invention. In particular, typical, but not limiting, amounts of reactive diluents are as follows by weight percent: 45%, 47%, 49%, 50%, 51%, 53%, 55%.
The photoinitiator can absorb energy in an ultraviolet light region or a visible light region to generate free radicals or cations, so that the polymerization, crosslinking and curing reaction of the monomers is initiated. In some embodiments, the photoinitiator is selected from at least one of acylphosphine oxide based photoinitiators, benzoin based photoinitiators, aminoalkyl phenone based photoinitiators, benzophenones, thioxanthone based photoinitiators, and iron arene based photoinitiators. Preferably, the acylphosphine oxide photoinitiator is selected from 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, diethyl 2,4, 6-trimethylbenzoylphosphonate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4 ', 4' -dimethyloctyl-2) phosphine oxide; the benzoin photoinitiator is at least one selected from benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; the amino alkyl benzophenone photoinitiator is selected from at least one of diphenylethanedione, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone; the thioxanthone photoinitiator is at least one selected from 2-chlorothianthrone, isopropyl thioxanthone and 2, 4-diethylthioxanthone. The addition amount of the photoinitiator is too much, so that the problems that a protective layer formed by the solder mask ink on a printed circuit board is too thick and easy to yellow and the like are easily caused, and the addition amounts of other components are correspondingly reduced, so that the performance of the protective layer is influenced; if the amount of the photoinitiator added is too small, the photocuring reaction may be incomplete, thereby affecting the performance of the resultant protective layer. Therefore, the embodiment of the invention controls the weight percentage of the photoinitiator in the solder mask ink to be 10-15%. In particular, typical, but not limiting, amounts of photoinitiator in weight percent are: 10%, 11%, 12%, 13%, 14%, 15%.
The nano color paste is used for color mixing, can be modulated according to the actual color requirement of the printed circuit board, and can be prepared by one or more of nano red, orange, yellow, green, cyan, blue, purple, black and the like during modulation. In the industry, green color is generally taken as the main material, and halogen-free nano phthalocyanine blue color paste and halogen-free nano permanent yellow color paste can be prepared according to the proportion. The actual color requirement of the printed circuit board can not be met when the addition amount of the nano color paste is too much or too little. Therefore, in the embodiment of the invention, the weight percentage of the nanometer color paste in the anti-welding ink is controlled to be 1-5%. Specifically, the typical, but not limiting, weight percentage of the nano color paste is as follows: 1%, 2%, 3%, 4%, 5%.
The auxiliary agent is mainly a leveling agent, so that the obtained solder mask ink can form a protective layer on the printed circuit board, and the protective layer has the advantages of flatness, smoothness and uniformity, and can be added or not according to actual conditions. In some embodiments, the adjuvant is selected from at least one of BYK-333, BYK-306, BYK-358N, BYK-310, BYK-354, BYK-356, BYK-300, TEGO 450, 410, 432, EFKA SL 3030, 3031, 3033, 3034, 3035, 3236, 3239, 3258, 3288 from BYK. The addition amount of the auxiliary agent is too much, and problems such as dripping, vortex eye and the like can occur; the addition amount of the auxiliary agent is too small, and the flatness and the smoothness of the obtained protective layer are not enough. Therefore, the weight percentage of the auxiliary agent in the solder mask ink is controlled to be 0% -1% in the embodiment of the invention.
Preferably, the viscosity of the solder mask ink is 5-10 mPa.s at 50 ℃, the surface tension is 20-34 mN/m, the particle size is less than 500nm, the viscosity of the solder mask ink with the performance parameters is low, the surface tension is enough, the ink-jet printing can be better realized, and the performance of forming a protective layer by curing the solder mask ink on a printed circuit board is better.
The embodiment of the invention provides a printed circuit board, which is provided with a protective layer, wherein the protective layer is obtained by printing the solder mask ink on the printed circuit board through a PCB digital ink-jet printer and then curing.
The printed circuit board has the advantages of adhesive force due to the protective layer formed by curing the solder resist ink, solvent resistance, acid resistance, alkali resistance, soldering resistance and electroplating resistance, and meets the requirements of IPC standard. In addition, the invention can form the protective layer in a digital ink-jet printing mode without the need of complex process flow required by the traditional solder mask ink, and has the advantages of high automation degree, environmental friendliness and cost reduction.
Preferably, the curing process of the protective layer is LED UV curing, and then the protective layer is thermally cured for 60min at 150 ℃ after characters are printed on the protective layer; wherein the main wavelength of the LED UV is 365nm and/or 395nm, and the curing energy is 1000mJ/cm2. Through solidifying protective layer UV earlier, make its preliminary fast curing surface dry type, adhesive force and the heat resistance of protective layer are strengthened to rethread thermal curing, help promoting the performance of gained protective layer.
In order to make the details and operation of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art, and to make the advanced performances of the modified acrylate resin of the embodiments of the present invention, the preparation method thereof, the solder resist ink and the printed circuit board obviously manifest, the above-mentioned technical solutions are exemplified by a plurality of examples below.
Example 1
A preparation method of a modified acrylate resin comprises the following steps:
(1) adding 240g of bisphenol A epoxy resin, 0.1g of hydroquinone, 0.05g of MEHQ, 0.6g N and N-dimethylaniline into a reaction kettle, stirring, heating to 80 ℃, and adding 56g of acrylic acid;
(2) when the temperature rises to 90 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, measuring the acid value once every half hour, stopping heating when AV is less than or equal to 1, adding 15g of tripropylene glycol diacrylate, continuing stirring, and discharging when the temperature is lower than 80 ℃ to obtain the modified acrylate resin (A1) with multiple active groups.
The obtained modified acrylate resin (A1) was combined with other components to prepare solder mask inks, the selection and amounts of each component are specified in Table 1.
Example 2
The preparation method of the modified acrylate resin in the embodiment is the same as that of the embodiment 1, except for the selection of other components and the use amount of each component in the preparation of the solder resist ink, which are detailed in table 1.
Example 3
The preparation method of the modified acrylate resin in the embodiment is the same as that of the embodiment 1, except for the selection of other components and the use amount of each component in the preparation of the solder resist ink, which are detailed in table 1.
Example 4
A preparation method of a modified acrylate resin comprises the following steps:
(1) adding 240g of novolac epoxy resin, 0.1g of hydroquinone and 0.6g of triphenylphosphine into a reaction kettle, stirring and heating to 80 ℃, and then adding 60g of acrylic acid;
(2) when the temperature rises to 85 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, 0.05g of MEHQ is added, the acid value is measured every half an hour, heating is stopped when AV is less than or equal to 1, 15g of neopentyl glycol di (methyl) acrylate is added and stirring is continued, and discharging is carried out when the temperature is lower than 80 ℃ to obtain the modified acrylate resin (A2) with multiple active groups.
The obtained modified acrylate resin (A2) was combined with other components to prepare solder mask inks, the selection and amounts of each component are specified in Table 1.
Example 5
The preparation method of the modified acrylate resin in this example is the same as that in example 4, except for the selection of other components and the amounts of the components in the preparation of the solder resist ink, which are detailed in table 1.
Example 6
The preparation method of the modified acrylate resin in this example is the same as that in example 4, except for the selection of other components and the amounts of the components in the preparation of the solder resist ink, which are detailed in table 1.
Example 7
A preparation method of a modified acrylate resin comprises the following steps:
(1) adding 246g of pentaerythritol tetraglycidyl ether, 0.12g of hydroquinone and 1.2g of triphenylphosphine into a reaction kettle, stirring and heating to 80 ℃, and then adding 60g of acrylic acid;
(2) when the temperature rises to 85 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, 0.06g of MEHQ is added, then the acid value is measured every half an hour, the heating is stopped when the AV is less than or equal to 1, and the material is discharged when the temperature is lower than 80 ℃, so that the modified acrylate resin (A3) with multiple active groups is obtained.
The obtained modified acrylate resin (A3) was combined with other components to prepare solder mask inks, the selection and amounts of each component are specified in Table 1.
Example 8
The preparation method of the modified acrylate resin in this example is the same as that of example 7, except for the selection of other components and the amounts of the components in the preparation of the solder resist ink, which are detailed in table 1.
Example 9
The preparation method of the modified acrylate resin in this example is the same as that of example 7, except for the selection of other components and the amounts of the components in the preparation of the solder resist ink, which are detailed in table 1.
TABLE 1 selection of ingredients and amounts (% by weight) of solder mask inks of examples 1-9
The components of examples 1 to 9 were mixed, stirred and dissolved, and then printed on a printed circuit board by a PCB digital inkjet printer, cured by LED UV, printed with characters, and then thermally cured at 150 ℃ for 60min to obtain a protective layer, and then tested for adhesion, solvent resistance, acid resistance, alkali resistance, soldering resistance, plating resistance (copper, pure tin, nickel, gold plating solutions), etc. according to IPC standards.
The specific test criteria are as follows:
1. testing the printing precision: and observing the diffusion conditions of the windowing position edge and the solder bridge resistance position ink by using a high power microscope, wherein the unilateral diffusion is less than or equal to 1.5mil, and the solder bridge resistance is less than or equal to 3mil to be regarded as OK.
2. And (3) testing the adhesive force: and (3) respectively scribing 11 scribing lines vertically and horizontally on the surface of the paint film by using a hundred-grid knife, wherein the length of the scribing line is about 20mm, and the depth is preferably the depth for scratching the paint layer. And slowly and flatly pasting one end of the 3M adhesive tape on the louver from the most edge of the louver, flatly pressing, waiting for 90 +/-30 seconds, then pressing the substrate (or the product) with the left hand, pinching the free end of the adhesive tape with the right hand, and quickly tearing off the 3M adhesive tape at about 180 degrees in the opposite direction. And carefully checking the falling condition of the coatings on the grids by using a magnifying glass, judging that the adhesion is OK if the falling area of the coatings is below 5%, and judging that the adhesion is NG if the falling area of the coatings is not more than 5%.
3. And (3) heat resistance test: and (3) coating the rosin type soldering flux on the surface of the printed and cured PCB, immersing the PCB in a lead-tin furnace at 288 ℃ for 10s, cooling, and repeating for many times until the PCB is torn and pulled for three times by using a 3M adhesive tape (model number 610#) and oil is removed. The heat resistance of the ink was measured by the number of times of heat resistance, and the standard was 3 times.
4. And (3) solvent resistance test: soaking in 25 deg.C alcohol for 1h, and determining that the adhesion test is OK, otherwise NG.
5. Acid resistance: 25 ℃ 10 vol% H2SO4Soaking for 30min, and determining that the adhesion test is OK, or NG.
6. Alkali resistance: soaking in 10 wt% NaOH at 25 deg.C for the required time for adhesion test NG. The criterion is 30min and < 30min is considered NG.
7. Plating resistance: the normal electroplating process (copper, pure tin, nickel, gold electroplating solution) test of the circuit board factory is OK.
The results are shown in Table 2.
Table 2 results of performance tests on protective layers obtained by ink-jet printing of solder mask inks obtained in examples 1 to 9 on PCB boards
As can be seen from the performance test results in Table 2, the solder mask inks obtained in the embodiments 1 to 9 of the invention can realize high-precision printing, the protective layer obtained by curing the solder mask inks on the printed circuit board through ink-jet printing has good adhesive force, and the heat resistance, the solvent resistance and the acid resistance of the solder mask inks meet the IPC industrial standard. Wherein the obtained solder resist ink has the following overall alkali resistance and electroplating property: examples 4-6 > examples 1-3 > examples 7-9, due to the inherent alkali and plating resistance of the structure of the host resin a used: a2 is more than A1 is more than A3, and A3 does not contain a chemical-resistant benzene ring structure; the main reasons for the poor alkali resistance and plating performance of examples 2-3, 5-6, and 8-9, respectively, relative to examples 1, 4, and 7, are that the functionality of the trifunctional aminoacrylate resin and pentaerythritol triacrylate used in examples 2-3, 5-6, and 8-9 is lower than that of the hexafunctional aminoacrylate resin and dipentaerythritol hexaacrylate used in examples 1, 4, and 7, and the crosslink density of the resulting protective layer after curing is insufficient to resist attack by plating chemicals; in addition, the A1 resin used in example 3 has better chemical resistance than the A3 resin used in example 7, but the A3 resin has lower viscosity than the A1 resin, so the effective addition amount of the A3 in the formulation is higher than that of the A1, which is why the alkali resistance and the plating performance of example 7 can also reach the levels of examples 2 and 3.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of modified acrylate resin is characterized by comprising the following steps:
the long-chain end epoxy resin and unsaturated unit carboxylic acid are subjected to ring-opening polymerization reaction to obtain the modified acrylate resin;
wherein the epoxy equivalent of the long-chain epoxy-terminated resin is 80-250 g/eq.
2. The method for preparing the modified acrylate resin according to claim 1 wherein the long-chain epoxy-terminated resin is at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, hydrogenated bisphenol A epoxy resin, triglycidyl-p-aminophenol, pentaerythritol tetraglycidyl ether.
3. The method for preparing a modified acrylate resin according to claim 1 wherein the unsaturated monocarboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and β -carboxyethyl (meth) acrylate.
4. The method for producing a modified acrylate resin according to claim 1 wherein the ring-opening polymerization is carried out in a reaction system containing an unsaturated monomer diluent; and/or
The ring-opening polymerization reaction is carried out in a reaction system containing an unsaturated monomer diluent, wherein the unsaturated monomer diluent is at least one selected from a monofunctional unsaturated monomer, a difunctional unsaturated monomer and a multifunctional unsaturated monomer.
5. The method for producing a modified acrylate resin according to any one of claims 1 to 4 wherein the ring-opening polymerization is carried out under catalysis of an esterification catalyst; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst, and the esterification catalyst is selected from at least one of tertiary amine esterification catalysts, quaternary ammonium salt esterification catalysts and phosphine esterification catalysts; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst, the esterification catalyst is selected from at least one of tertiary amine esterification catalysts, quaternary ammonium salt esterification catalysts and phosphine esterification catalysts, and the tertiary amine esterification catalyst is selected from at least one of triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst, the esterification catalyst is selected from at least one of a tertiary amine esterification catalyst, a quaternary ammonium salt esterification catalyst and a phosphine esterification catalyst, and the quaternary ammonium salt esterification catalyst is selected from at least one of trimethyl benzyl ammonium chloride, methyl triethyl ammonium chloride and hexadecyl trimethyl ammonium bromide; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst, wherein the esterification catalyst is selected from at least one of tertiary amine esterification catalysts, quaternary ammonium salt esterification catalysts and phosphine esterification catalysts, and the phosphine esterification catalyst is selected from at least one of triphenylphosphine, tributylphosphine, triethylphosphine, tri-o-toluyl phosphine, tri-m-toluyl phosphine, tri-p-phenyl-formyl phosphine and tri (p-methoxyphenyl) phosphine; and/or
A polymerization inhibitor is also added in the ring-opening polymerization reaction; and/or
The ring-opening polymerization reaction is also added with a polymerization inhibitor, and the polymerization inhibitor is selected from at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone and p-hydroxyanisole.
6. The modified acrylate resin prepared by the method for preparing the modified acrylate resin according to any one of claims 1 to 5, wherein the modified acrylate resin is in a liquid state, the epoxy equivalent weight of the modified acrylate resin is 200g/eq to 500g/eq, and the viscosity of the modified acrylate resin is less than 20000 mPa.s.
7. The solder mask ink is characterized by comprising the following components in percentage by weight, based on 100% of the total weight of the solder mask ink:
8. the solder mask ink of claim 7, wherein the solder mask ink has a viscosity of 5 to 10mpa.s at 50 ℃, a surface tension of 20 to 34mN/m, and a particle size of < 500 nm.
9. The solder resist ink of claim 7, wherein the multifunctional acrylate is at least one selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate; and/or
The acrylic resin is selected from trifunctional amino acrylate resin, hexafunctional amino acrylate resin and hexafunctional polyurethane acrylate resin; and/or
The curing agent is selected from at least one of diaminodiphenyl sulfone, 4' diaminodiphenylmethane, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, boron trifluoride-amine complex, cationic initiator, iodohexafluoroantimonate, (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluoroantimonate, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile), blocked isocyanate; and/or
The active diluent is at least one selected from 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, isobornyl (methyl) acrylate, (2-ethyl-2-methyl-1, 3-dioxolanyl-4) acrylate, (2-isopropyl-2-methyl-1, 3-dioxolanyl-4) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl alicyclic epoxy resin, alicyclic epoxy acrylate and alicyclic epoxy methacrylate; and/or
The photoinitiator is at least one selected from an acylphosphine oxide photoinitiator, a benzoin photoinitiator, an amino alkyl benzophenone photoinitiator, benzophenone, a thioxanthone photoinitiator and an iron arene photoinitiator.
10. A printed circuit board, wherein a protective layer is disposed on the printed circuit board, and the protective layer is obtained by inkjet printing the solder mask ink according to any one of claims 7 to 9 on the printed circuit board and curing the ink.
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| CN114149548A (en) * | 2021-12-15 | 2022-03-08 | 厦门格林泰新材料科技有限公司 | Flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from same |
| CN114773905A (en) * | 2022-04-15 | 2022-07-22 | 华南理工大学 | White UV/thermal dual-curing FPC inkjet character ink and preparation method thereof |
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| CN114773905A (en) * | 2022-04-15 | 2022-07-22 | 华南理工大学 | White UV/thermal dual-curing FPC inkjet character ink and preparation method thereof |
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Application publication date: 20210625 |