CN117706870A - Photosensitive solder resist resin composition, photosensitive solder resist insulating film and electronic component - Google Patents
Photosensitive solder resist resin composition, photosensitive solder resist insulating film and electronic component Download PDFInfo
- Publication number
- CN117706870A CN117706870A CN202311615350.4A CN202311615350A CN117706870A CN 117706870 A CN117706870 A CN 117706870A CN 202311615350 A CN202311615350 A CN 202311615350A CN 117706870 A CN117706870 A CN 117706870A
- Authority
- CN
- China
- Prior art keywords
- solder resist
- resin composition
- photosensitive solder
- insulating film
- group
- 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
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 81
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000004593 Epoxy Substances 0.000 claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 37
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- -1 alkyl benzene ketone compounds Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
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- 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 12
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 125000003282 alkyl amino group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 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 8
- 239000003086 colorant Substances 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
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- 229960002130 benzoin Drugs 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019382 gum benzoic Nutrition 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
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- 235000010290 biphenyl Nutrition 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- 150000003839 salts Chemical class 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 1
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 11
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- 239000003999 initiator Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 15
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 14
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 11
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- 229910052739 hydrogen Inorganic materials 0.000 description 7
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- 238000007789 sealing Methods 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 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
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- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-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
- IQYWSAQGMJBBCZ-UHFFFAOYSA-N 2-(1-ethoxy-1-propoxyethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound C(C)OC(C(CO)(CO)CO)(C)OCCC IQYWSAQGMJBBCZ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 1
- LPKFUUCTGPTWBH-UHFFFAOYSA-N 4-ethoxy-2-nonyl-3-propoxyphenol Chemical compound C(C)OC1=C(C(=C(C=C1)O)CCCCCCCCC)OCCC LPKFUUCTGPTWBH-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-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
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a photosensitive solder resist resin composition, a photosensitive solder resist insulating film and an electronic component. The photosensitive solder resist composition comprises, by mass, 100 parts of alkali-soluble epoxy acrylic resin, 10-50 parts of nitrogen-containing six-membered heterocyclic compound and 0.1-5 parts of photoinitiator. The photosensitive solder resist resin composition provided by the application is matched with the alkali-soluble epoxy acrylic resin, at least one six-membered heterocyclic compound and the photoinitiator, so that the heat resistance and the adhesive force of the photosensitive solder resist insulating film are improved, undercut can be reduced, side erosion is reduced, and meanwhile, the photosensitive solder resist resin composition also has excellent nickel-gold plating performance and wide application prospect.
Description
Technical Field
The invention relates to the technical field of resin compositions, in particular to a photosensitive solder resist resin composition, a photosensitive solder resist insulating film and an electronic element.
Background
As the wiring density, fineness and integration level of PCBs (printed wiring boards) are becoming higher and higher, the conductor circuit pattern pitch of the printed wiring boards is becoming finer and finer in order to meet the demands for high-density formulation of small electronic components. In addition, small-sized beads in the fields of miniLEDs and microLEDs are also required to have small and dense windows, and correspondingly, the requirements on heat resistance, nickel-gold melting and the like of the solder resist insulating film are also higher.
In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly aims to provide a photosensitive solder resist resin composition, a photosensitive solder resist insulating film and an electronic element, so as to solve the problem that the performances of heat resistance, nickel-gold and the like of the solder resist insulating film in the prior art cannot meet the requirements of the printed circuit board, miniLED and microLED display fields.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photosensitive solder resist resin composition comprising, in parts by mass, 100 parts of an alkali-soluble epoxy acrylic resin, 10 to 50 parts of a nitrogen-containing six-membered heterocyclic compound and 0.1 to 5 parts of a photoinitiator; wherein the nitrogen-containing six-membered heterocyclic compound is selected from at least one of structural compounds shown in the following formula (A) or formula (B);
wherein at least one of the end groups of Ra, rb and Rc is vinyl, ethynyl, amino or epoxy; at least one of the end groups Rd, re and Rf is vinyl, ethynyl, amino or epoxy.
Further, at least one of Ra, rb, rc is alkylvinyl, alkylethynyl, alkylamino, alkylepoxy, at least one of Rd, re, rf is alkylvinyl, alkylethynyl, alkylamino, alkylepoxy, wherein each of alkylvinyl, alkylethynyl, alkylamino, alkylepoxy is independently represented by R 1 R 2 ，R 2 Selected from vinyl, ethynyl, amino or epoxy groups; wherein R1 is selected from a direct bond, a C1-C10 linear or branched alkylene group, and carbon atoms and hydrogen atoms in the alkylene group are respectively and selectively replaced by S or O;
further, R 1 Selected from direct bond, C1-C5 straight chain or branched chain alkylene.
Further, the nitrogen-containing six-membered heterocyclic compound is a compound shown in a formula (A), at least one of terminal groups of Ra, rb and Rc is epoxy, and at least one of the terminal groups is vinyl, ethynyl or allyl;
further, the nitrogen-containing six-membered heterocyclic compound is a compound shown in a formula (B), at least one of end groups of Rd, re and Rf is epoxy group, and at least one of the end groups is vinyl, ethynyl or allyl.
Further, the nitrogen-containing six-membered hetero compound includes a compound represented by the formula (A) and a compound represented by the formula (B), and the mass ratio of the compound represented by the formula (A) to the compound represented by the formula (B) is 1 to 49:1 to 49, preferably 1 to 9:9 to 1, and preferably 1 to 9:9 to 1; wherein at least one of the terminal groups Ra, rb, rc is vinyl, allyl or ethynyl, preferably each of the terminal groups Ra, rb, rc is independently vinyl, allyl or ethynyl; at least one of the end groups Rd, re, rf is an epoxy group, preferably each of the end groups Rd, re, rf is independently an epoxy group.
Further, the nitrogen-containing six-membered heterocyclic compound is selected from at least one of the following formulas (a) to (d):
further, the alkali-soluble epoxy acrylic resin comprises at least one of a carboxylic acid modified bisphenol A type epoxy resin, a carboxylic acid modified bisphenol F type epoxy resin, a carboxylic acid modified bisphenol S type epoxy resin, and a carboxylic acid modified phenolic epoxy resin, and has an acid value of 50-100 mgKOH/g and a solid content of 40-50 wt%.
Further, the photoinitiator is selected from at least one of a radical polymerization photoinitiator or a cationic polymerization photoinitiator.
Further, the free radical polymerization photoinitiator is at least one selected from benzoin and derivatives, alkyl benzene ketone compounds, acyl phosphine oxides, diphenyl ketone compounds and thioxanthone compounds.
Further, the cationic polymerization photoinitiator is selected from at least one of diaryl iodonium salt, triaryliodonium salt, alkyl iodonium salt and isopropylbenzene ferrocene hexafluorophosphate.
Further, the resin composition further comprises a thermosetting agent, the thermosetting agent comprises at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin and alicyclic type epoxy resin, and the epoxy equivalent of the thermosetting agent is 100-400 g/eq.
Further, the resin composition further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of a toughening agent, a dispersing agent, a leveling agent, a defoaming agent and a coloring agent.
Further, the amount of the toughening agent is 0 to 10 parts by mass.
Further, the dispersant, the leveling agent, the antifoaming agent, and the colorant are each independently used in an amount of 0 to 1 part by mass.
In order to achieve the above object, according to another aspect of the present invention, there is provided a solder resist insulating film, the material of which is the solder resist resin composition provided in the above first aspect.
According to another aspect of the present invention, there is also provided an electronic component comprising the photosensitive resist insulating film provided in the second aspect or a hardened film formed by curing the photosensitive solder resist insulating film provided in the second aspect.
By applying the technical scheme, the photosensitive solder resist resin composition provided by the application is matched with the alkali-soluble epoxy acrylic resin, at least one six-membered heterocyclic compound and the photoinitiator, so that the heat resistance and the adhesive force of the photosensitive solder resist insulating film are improved, undercut and side erosion can be reduced, excellent nickel-gold plating performance is achieved, and the application prospect is wide.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background art of the application, the distance between the conductive circuit patterns of the existing printed circuit board is finer and finer, and small-size lamp beads in the fields of minileds and microleds are also required to be small and dense in window opening, and correspondingly, the requirements on heat resistance, nickel-gold melting and the like of the solder resist insulating film are also higher. In order to meet the requirements of the printed circuit board, miniLED and microLED display fields on performances such as resolution, heat resistance, nickel-gold melting and the like of a solder resist insulating film, the application provides a photosensitive solder resist resin composition, a photosensitive solder resist insulating film and an electronic element.
In a first exemplary embodiment of the present application, there is provided a photosensitive resist resin composition comprising 100 parts by mass of an alkali-soluble epoxy acrylic resin, 10 to 50 parts by mass of a nitrogen-containing six-membered heterocyclic compound and 0.1 to 5 parts by mass of a photoinitiator; wherein the nitrogen-containing six-membered heterocyclic compound is selected from at least one of structural compounds represented by the following formula (A) or (B):
wherein at least one of the end groups of Ra, rb and Rc is vinyl, ethynyl, amino or epoxy; at least one of the end groups Rd, re and Rf is vinyl, ethynyl, amino or epoxy.
By applying the technical scheme, the photosensitive solder resist resin composition provided by the application is matched with the alkali-soluble epoxy acrylic resin, at least one nitrogenous six-membered heterocyclic compound and the photoinitiator, so that the heat resistance and the adhesive force of the photosensitive solder resist insulating film are improved, undercut and side erosion can be reduced, and meanwhile, the photosensitive solder resist resin composition also has excellent nickel-gold plating performance and wide application prospect.
[ Nitrogen-containing six-membered heterocyclic Compound ]
The nitrogen-containing six-membered heterocyclic compounds provided herein have at least one terminal group that is readily reactive, capable of participating in polymerization reactions in the composition under light or heat conditions, while also improving adhesion to a substrate. Compared with the traditional benzotriazole compounds, 3-methylbenzothiazole-2-thioketone and benzimidazole compounds, the adhesive has better sealing effect with the base material. This is because the at least one nitrogen-containing six-membered heterocyclic compound provided by the present application can participate in polymerization reaction by using at least one terminal group, and the introduction of a rigid nitrogen-containing six-membered heterocyclic ring into the molecular chain of the solder resist insulating film can improve heat resistance; when two or more end groups participate in the reaction, a crosslinked network with compact structure can be formed, and the film is endowed with excellent heat resistance and acid and alkali corrosion resistance. In addition, the nitrogen-containing six-membered heterocyclic ring can also form a hydrogen bond network with the base material to construct another re-crosslinking network, and form a large number of riveting points with the base material by utilizing the hydrogen bond action, so that the adhesive force with the base material is further improved.
In order to further improve the heat resistance of the photosensitive solder resist insulating film, in some embodiments of the present application, at least one of Ra, rb, rc is an alkyl vinyl group, an alkyl acetylene group, an alkylamino group, an alkyl epoxy group, and at least one of Rd, re, rf is an alkyl vinyl group, an alkyl acetylene group, an alkylamino group, an alkyl epoxy group; wherein each of the alkyl vinyl, alkyl ethynyl, alkyl amino, alkyl epoxy groups is independently represented by R 1 R 2 ，R 2 Selected from vinyl, ethynyl, amino or epoxy groups; wherein represents a bond to a nitrogen-containing six-membered heterocyclic ring, R1 is selected from a direct bond, a C1-C10 linear or branched alkylene group, and wherein the carbon and hydrogen atoms are optionally substituted with S or O, respectively.
The above-mentioned C1-C10 straight-chain or branched alkylene group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl and the like.
In the above carbon atoms and hydrogen atoms which are optionally substituted with S or O, the carbon atom substituted with S or O may be a carbon atom in the main chain or a carbon atom in the side chain; when O is used to replace a hydrogen atom, O and C can be connected by a single bond or a double bond.
In other embodiments of the present application, to increase the crosslink density, R1 is selected from a direct bond, a C1 to C5 linear or branched alkylene group, and when the carbon atom and the hydrogen atom thereof are optionally substituted with S or O, respectively, the polarity of the nitrogen-containing six-membered heterocyclic compound is enhanced, and more hydrogen bonds are formed between the photosensitive solder resist insulating film and the substrate, thereby further improving the adhesion.
To further enhance the compactness of the crosslinked network, in some embodiments, the nitrogen-containing six-membered heterocyclic compound is a compound of formula (a), at least one of the terminal groups Ra, rb, rc is an epoxy group, and at least one is an vinyl, ethynyl, or allyl group. At least two groups which are easy to react in the formula (A) can participate in photopolymerization reaction of the solder resist insulating film in an exposure stage and crosslinking reaction in a heat curing stage to form a more compact crosslinking network, so that the heat resistance and acid and alkali corrosion resistance are further improved; the nitrogen-containing six-membered heterocycle can form a hydrogen bond network with the base material, so that the adhesive force with the base material is further improved, and the sealing effect with the base material is better.
In order to further enhance the compactness of the crosslinked network, in other embodiments, the nitrogen-containing six-membered heterocyclic compound is a compound of formula (B), at least one of the end groups Rd, re, rf is an epoxy group, and at least one is an vinyl, ethynyl or allyl group. At least two groups which are easy to react in the formula (B) can participate in photopolymerization reaction of the solder resist insulating film in an exposure stage and crosslinking reaction in a heat curing stage to form a more compact crosslinking network, so that the heat resistance and acid and alkali corrosion resistance are further improved; the nitrogen-containing six-membered heterocycle can form a hydrogen bond network with the base material, so that the adhesive force with the base material is further improved, and the sealing effect with the base material is better.
In order to further enhance the compactness of the crosslinked network, in other embodiments, the nitrogen-containing six-membered heterocyclic compound includes at least one of the compounds represented by formula (a) and at least one of the compounds represented by formula (B), preferably at least one of the terminal groups Ra, rb, rc is vinyl, allyl or ethynyl, and at least one of the terminal groups Rd, re, rf is epoxy; the corrosion resistance and the heat resistance can be improved by introducing two different nitrogen-containing six-membered heterocycles to form a double cross-linked network; the nitrogen-containing six-membered heterocyclic rings on the first and second re-crosslinking networks can form a hydrogen bond network with the base material, a third and fourth re-weak crosslinking networks are constructed, and the two re-weak crosslinking networks form a large number of riveting points with the base material by utilizing the hydrogen bond effect, so that the adhesive force with the base material is further improved.
The terminal groups of Ra, rb and Rc may be the same or different, and the terminal groups of Rd, re and Rf may be the same or different.
When the end groups of Ra, rb and Rc are respectively and independently selected from vinyl, propenyl or ethynyl, and the end groups of Rd, re and Rf are respectively and independently selected from epoxy groups, the formation of multiple networks by using different end groups is facilitated, and the compactness of the crosslinked network is further improved.
In some embodiments of the present application, in order to further increase the crosslink density of the photosensitive resist insulating film formed from the resin composition, it is preferable that the mass ratio of the compound represented by formula (a) to the compound represented by formula (B) is 1 to 49:1 to 49, and especially when the mass ratio of the compound represented by formula (a) to the compound represented by formula (B) is 1 to 9:9 to 1, the crosslink density of the formed photosensitive resist insulating film is denser.
Typically, but not by way of limitation, the mass of the compound of formula (A) and the compound of formula (B) is, for example, 1:49:2:48:5:45, 8:42, 10:40, 15:35, 20:30, 25:25, 30:20, 35:15, 40:10, 45:5, 49:1 or any two values. In some embodiments of the present application, the nitrogen-containing six-membered heterocyclic compound is selected from at least one of the following formulas (a) to (d):
[ alkali-soluble epoxy acrylic resin ]
The specific type of the alkali-soluble epoxy acrylic resin is not limited, and alkali-soluble epoxy acrylic resins commonly used in the art may include, but are not limited to, any of carboxylic acid-modified bisphenol a-type epoxy resins, carboxylic acid-modified bisphenol F-type epoxy resins, carboxylic acid-modified bisphenol S-type epoxy resins, carboxylic acid-modified phenolic epoxy resins. In order to further improve the acid-alkali resistance of the photosensitive solder resist insulating film, it is preferable that the acid value of the alkali-soluble epoxy acrylic resin is 50 to 100mg KOH/g (e.g., 50mg KOH/g, 55mg KOH/g, 60mg KOH/g, 65mg KOH/g, 70KOH mg/g, 75mg KOH/g, 80mg KOH/g, 90mg KOH/g, 100mg KOH/g), and particularly when the acid value of the alkali-soluble epoxy acrylic resin is 80 to 120mg KOH/g, the photosensitive solder resist insulating film formed thereof has more excellent acid-alkali resistance.
[ photoinitiator ]
The specific type of the above photoinitiator is not limited, and any photoinitiator commonly used in the art may be used, including, but not limited to, any one or a mixture of two or more of a radical polymerization photoinitiator or a cationic polymerization photoinitiator.
The above-mentioned radical polymerization photoinitiator may be a cleavage initiator such as benzoin and derivatives (benzoin, benzoin dimethyl ether, benzoin diethyl ether, benzoin isopropyl ether, benzoin butyl ether), alkylbenzene compounds (α, α -diethoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylphenone), acylphosphorus oxides (aroylphosphine oxide, bisbenzoylphenylphosphine oxide), and the like, such as IGM 651, 184, TPO, 819, 907, and the like; or a hydrogen abstraction photoinitiator such as benzophenone (benzophenone, 2, 4-dihydroxybenzophenone, michler's ketone), thioxanthone (thiopropylthioxanthone, isopropylthioxanthone), etc., for example ITX, DETX, BP.
The cationic polymerization photoinitiator includes, but is not limited to, any one or a mixture of two or more of diaryliodonium salts, triaryliodonium salts, alkyl iodonium salts, isopropylbenzene ferrocenium hexafluorophosphate, and the like.
[ Heat curing agent ]
The nitrogen-containing six-membered heterocyclic compound having an epoxy group in the terminal group can function as a thermosetting agent. In some embodiments, the above resin composition may further include a heat curing agent, the specific type of which is not limited, and curing agents commonly used in the art may include any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, and alicyclic type epoxy resin, but are not limited thereto. Especially, when the epoxy resin used as the curing agent has an epoxy equivalent of 100-400 g/eq (such as 100g/eq, 150g/eq, 200g/eq, 250g/eq, 300g/eq, 350g/eq, 400 g/eq), the curing efficiency and the heat resistance of the formed photosensitive solder resist insulating film are improved.
[ photopolymerization monomer ]
The alkali-soluble epoxy acrylic resin carries a certain number of double bonds, and can be subjected to photo-curing reaction in the exposure process and used as a macromolecular photopolymerization monomer; the nitrogen-containing six-membered heterocyclic compound with the end group containing unsaturated double bonds and triple bonds can participate in photocuring reaction and be used as a photopolymerization monomer. In order to further increase the speed of the photo-curing reaction and reduce the viscosity of the resin composition, the above resin composition may further include other reactive diluents as photo-polymerizable monomers. The reactive diluents include monofunctional (meth) acrylates such as (ethoxy) phenol (meth) acrylate, stearic acid acrylate, ethoxy (propoxy) nonylphenol (meth) acrylate, ethoxy (propoxy) tetrahydrofurfuryl (meth) acrylate, 1, 6-hexanediol diacrylate, tricyclodecanedimethanol diacrylate, dioxane glycol diacrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, difunctional (meth) acrylates such as polyethylene glycol (400) diacrylate, polypropylene glycol (600) diacrylate, trifunctional (meth) acrylates such as ethoxy (propoxy) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.
[ auxiliary agent ]
In order to further improve the overall properties of the photosensitive solder resist insulating film, it is preferable that an auxiliary agent including, but not limited to, any one or two or more of a toughening agent, a dispersing agent, a leveling agent, a defoaming agent, or a coloring agent is further included in the above resin composition.
In order to further improve the bendability of the photosensitive solder resist insulating film, it is preferable that the resin composition further comprises 0 to 10 parts of a toughening agent based on 100 parts by mass of the alkali-soluble epoxy acrylic resin. The toughening agent comprises one or more of core-shell rubber toughened epoxy resin, thermoplastic elastomer, polyurethane elastomer and rubber powder. As the core-shell rubber toughening epoxy resin, kaneka's MX154, MX113, MX158, M257 and the like can be used as the commercial products. The thermoplastic elastomer may be a styrene-butadiene block copolymer (SBS), a styrene-poly (ethylene-ethylene/propylene) block-polystyrene (SEEPS), a styrene-isoprene-styrene block copolymer (SIS), or the like; as the polyurethane elastomer, commercially available products such as Artpearl C-300T, artpearl C-400T, artpearl C-600T, artpearl SE-050T, artpearl GR-50W and the like of RHC-730,Negami Chemical Industry of Dainichiseika can be used; as the commercial product of the rubber powder, kaneka's MZ100, MZ 210, MZ711 and the like can be used.
In order to further improve the wettability and dispersibility of the photosensitive solder resist insulating film, it is preferable that the resin composition further comprises 0 to 1 part of a dispersant based on 100 parts by mass of the alkali-soluble epoxy acrylic resin. As the dispersant, known dispersants such as polyester propionate-based dispersants, silicone resin-based dispersants, and fluorosurfactant-based dispersants can be used, and commercially available products include BYK9077, BYK110, BYK168, SDA-2, SDA-3, HLD-6, etc.;
in order to further improve the film forming property of the photosensitive solder resist insulating film, it is preferable that the resin composition further comprises 0 to 1 part of a leveling agent based on 100 parts by mass of the alkali-soluble epoxy acrylic resin. As the leveling agent, known leveling agents such as polyester acrylate leveling agents and silicone resin leveling agents can be used, and commercially available products include BYK394, BYK322, BYK UV3530, efka FL 3740, modarez PW 336 and the like.
In order to further improve the stability of the solder resist insulating film, it is preferable that the resin composition further comprises 0 to 1 part of an antifoaming agent based on 100 parts by mass of the alkali-soluble epoxy acrylic resin. As the defoaming agent, known ones such as polysiloxanes, polyolefins, polyethers, and polyacrylates are used, and commercially available ones include BYK015, BYK1730, BYK354, GPE-3000, defom 5300, and Defom 6800.
In order to further improve the aesthetic property of the solder resist insulating film, the resin composition preferably further comprises 0 to 1 part of a colorant based on 100 parts by mass of the soluble epoxy acrylic resin. As the colorant, known colorants can be used, and commercially available products include MA7, K8730, R706, and the like.
In a second exemplary embodiment of the present application, there is also provided a photosensitive resist insulating film, the material of which is any one of the photosensitive resist resin compositions provided in the first exemplary embodiment.
The photosensitive solder resist insulating film provided by the application is matched with the alkali-soluble epoxy acrylic resin and the initiator by introducing the nitrogenous six-membered heterocyclic compound, so that the heat resistance and the adhesive force are remarkably improved, the undercut is reduced, the side etching is reduced, and meanwhile, the photosensitive solder resist insulating film also has excellent nickel-gold plating performance and has a wide application prospect.
In a third exemplary embodiment of the present application, there is also provided an electronic component including the photosensitive solder resist insulating film provided in the second exemplary embodiment.
The electronic element provided by the application has more excellent heat-resistant stability and acid and alkali resistance by adopting the photosensitive solder mask insulating film.
The advantageous effects of the present application are further described below with reference to examples and comparative examples.
Example 1
This example provides a photosensitive resist resin composition comprising 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content 45%), 1.0g of triallyl isocyanurate, 9.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin advanced New materials Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basf).
Example 2
This example provides a photosensitive resist resin composition comprising 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content 45%), 9.0g of triallyl isocyanurate, 1.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin advanced New materials Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basf).
Example 3
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 49.0g of triallyl isocyanurate, 1.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basf).
Example 4
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 1.0g of triallyl isocyanurate, 49.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi Japan), 4.0g of dispersant (EFKA-4310, basv).
Example 5
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 6.0g of triallyl isocyanurate, 10.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basv).
Example 6
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 6.0g of triallyl isocyanurate, 10.0g of triglycidyl isocyanurate, 0.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of phthalocyanine green (K8730, basoff), and 0.2g of dispersant (BYK 161).
Example 7
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 6.0g of triallyl isocyanurate, 10.0g of triglycidyl isocyanurate, 5.0g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 90.0g of titanium pigment (R706, duPont) and 1.0g of dispersant (BYK 110).
Example 8
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 6.0g of triallyl isocyanurate, 4.0g of dipentaerythritol acrylic acid ester (DPHA, sand-dame), 10.0g of triglycidyl isocyanurate, 5.0g of bisphenol A epoxy resin (128E, nanya), 5.0g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 90.0g of titanium pigment (R706, duPont) and 1.0g of dispersant (BYK 110).
Example 9
This example differs from example 5 in that triallyl cyanurate is replaced with a compound represented by the following formula (d).
Example 10
This example differs from example 5 in that triallyl cyanurate is replaced with a compound represented by the following formula (c).
Example 11
This example differs from example 5 in that the compound of formula (c) is used instead of triglycidyl isocyanurate.
Example 12
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 50.0g of triallyl isocyanurate, 5.0g of bisphenol A epoxy resin (128E, nanya), 2.5g of photopolymerization initiator (TPO, tianjin Jiujia New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan) and 4.0g of dispersant (EFKA-4310, basff).
Example 13
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 50.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basv).
Example 14
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 10.0g of triallyl isocyanurate, 5.0g of bisphenol A epoxy resin (128E, nanya), 2.5g of photopolymerization initiator (TPO, tianjin Jiujia New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan) and 4.0g of dispersant (EFKA-4310, basff).
Example 15
The present embodiment provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 10.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of MA7 (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basv).
Example 16
This example differs from example 5 in that 3, 5-tetramethyl biphenol diglycidyl ester was used instead of triglycidyl isocyanurate.
Comparative example 1
The present comparative example provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content 45%), 6.0g of dipentaerythritol acrylate (DPHA, sand-damax), 10.0g of biphenyl crystalline epoxy resin (YX-4000, mitsubishi Japan), 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi Japan), 4.0g of dispersant (EFKA-4310, basv).
Comparative example 2
The present comparative example provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 2.0g of triallyl isocyanurate, 5.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basv).
Comparative example 3
The present comparative example provides a photosensitive solder resist resin composition comprising: 100.0g of alkali-soluble epoxy acrylic resin ACAZ250 (acid value: 70mgKOH/g, solid content: 45%), 24.0g of triallyl isocyanurate, 40.0g of triglycidyl isocyanurate, 2.5g of photopolymerization initiator (TPO, tianjin New Material Co., ltd.), 5.0g of carbon black (MA 7, mitsubishi, japan), 4.0g of dispersant (EFKA-4310, basv).
Comparative example 4
This comparative example differs from example 5 in that divinyl ether is used in place of the nitrogen-containing six-membered heterocyclic compound.
Test examples
The photosensitive resist resin compositions provided in the above examples and comparative examples were prepared into photosensitive resist insulating films, respectively, and then the solder heat resistance, the solder resist adhesion, the nickel-gold adhesion and undercut (undercut) of the photosensitive resist insulating films were evaluated, respectively, and the results are shown in table 1 below.
Wherein, (1) the preparation method of the photosensitive solder resist insulating film comprises the following steps:
[ 1 coating Process ]
The solder resist composition was formed (coated and dried) on a support film (base layer), and an applicator, a bar coater, a wire wound bar coater, a roll coater, and a curtain coater were used for coating. The coating thickness is 10-60 mu m. The material of the base material layer is preferably polyethylene terephthalate (PET) or Polycarbonate (PC).
[ 2 drying Process ]
And (3) placing the support film coated with the solder mask composition into an electrothermal blowing drying box, and drying to remove the solvent to form a dry film of the solder mask. The drying temperature of the oven is preferably below 100 ℃, preferably 85 ℃ and the drying time is 15-45 min, and the drying time is 85 ℃ and 30min.
[ 3 film-sticking Process ]
The pre-dried solder resist dry film is pseudo-adhered on the surface of a PCB or an IC carrier plate, and then the solder resist dry film is compacted by a vacuum film sticking machine to form a laminate sample of a supporting film, a solder resist layer and a copper-clad plate; this process ensures complete venting of the air bubbles between the lines.
[ 4 Exposure procedure ]
The composition is selectively exposed to light, and a suitable film or LDI design is selected according to the target pattern, and the composition can be exposed by a high-pressure mercury lamp, an LED (light-emitting diode) exposure machine, an LDI exposure machine, an ultrahigh-pressure mercury lamp, a xenon lamp and a carbon arc lamp, wherein the exposure energy is 400mJ/cm 2 。
[ 5 ] development Process
Developing means that unexposed parts of the solder mask dry film in the exposure process are dissolved by an alkaline developer, and the exposed parts remain unchanged. The unexposed areas are soluble, the exposed areas are insoluble, and the difference in solubility before and after exposure is critical for development. Either horizontal development or vertical development may be employed. The concentration, temperature and development time of the developer are very important, and if the concentration is too high or the temperature is too high, the developer may dissolve the photosensitive adhesive layer too strongly, causing deformation or distortion of the circuit pattern. If the concentration is too low or the temperature is too low, the developing solution is not effective to dissolve the unexposed portions, resulting in unclear or incomplete circuit patterns. The developing solution is recommended to be 1wt% sodium carbonate aqueous solution or 1wt% potassium carbonate aqueous solution, the developing temperature is recommended to be 28-32 ℃, and the developing pressure is recommended to be 0.2-0.4 MPa.
[ 6 Heat curing (curing) procedure ]
The developed dry film resist is heated and cured to form a patterned cured product, the heat curing temperature is suggested to be 125-165 ℃, and the heat curing time is suggested to be 0.5-1 h.
The thermal curing temperature in this application was selected to be 150℃and the thermal curing time was 1h.
(2) The method for evaluating soldering heat resistance comprises the following steps: dipping a substrate with a photosensitive solder resist insulating film in rosin for 5s, and then immersing the substrate in a 288 ℃ tin furnace for 10s; observing whether the surface is layered, discolored and foamed; if no abnormality occurs in appearance, the above operation is repeated, and the maximum number of times that can be repeated is recorded.
(3) The evaluation method of the anti-welding adhesive force comprises the following steps: drawing a hundred cells on the surface of the photosensitive solder resist insulating film by using a hundred cell knife, and then pulling up the photosensitive solder resist insulating film by using a 3M 600 adhesive tape by 90 degrees to see whether the photosensitive solder resist insulating film falls off or not, wherein a new adhesive tape is required to be replaced each time; if no abnormality occurs, repeatedly pulling up by 90 degrees with a 3M 600 adhesive tape for 3 times; if there is abnormality, record what times the ink comes off.
(4) Adhesion of nickel-gold: firstly, carrying out nickel-gold surface treatment on the surface of a photosensitive solder resist insulating film [ degreasing, washing, microetching, washing, pickling, presoaking, activating nickel, washing, post-soaking, washing, soaking nickel, washing and drying ], and then scribing a hundred lattice on the surface treated by the nickel-gold surface by using a hundred lattice knife; then the 3M 600 adhesive tape is pulled up by 90 degrees to see whether the adhesive tape falls off or not, and a new adhesive tape needs to be replaced every time; if no abnormality occurs, repeatedly pulling up by 90 degrees with a 3M 600 adhesive tape for 3 times; if there is abnormality, record what times the ink comes off.
(5) Undercut (undercut): line width/line spacing are adopted as L/d respectively: a 50 μm/50 μm film is used for manufacturing a photosensitive solder resist insulating film into a circuit pattern; slicing the circuit pattern, observing the section by using a metallographic microscope to obtain the side etching size and recording the data.
TABLE 1
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the photosensitive solder resist insulating film provided by the application is matched with the alkali-soluble epoxy acrylic resin and the initiator by introducing the nitrogenous six-membered heterocyclic compound, so that the heat resistance and the adhesive force are remarkably improved, the undercut is reduced, the side etching is reduced, and meanwhile, the photosensitive solder resist insulating film also has excellent nickel-gold plating performance and has a wide application prospect.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The photosensitive solder resist resin composition is characterized by comprising, by mass, 100 parts of alkali-soluble epoxy acrylic resin, 10-50 parts of nitrogen-containing six-membered heterocyclic compound and 0.1-5 parts of photoinitiator; wherein the nitrogen-containing six-membered heterocyclic compound is selected from at least one of structural compounds shown in the following formula (A) or formula (B):
wherein at least one of the end groups of Ra, rb and Rc is vinyl, ethynyl, amino or epoxy; at least one of the end groups Rd, re and Rf is vinyl, ethynyl, amino or epoxy.
2. The resin composition according to claim 1, wherein at least one of Ra, rb, and Rc is an alkylvinyl group, an alkylethynyl group, an alkylamino group, or an alkylepoxy group; and at least one of the Rd, the Re and the Rf is alkyl vinyl or alkyl ethylAlkynyl, alkylamino, alkyl epoxy; wherein each of the alkylvinyl group, the alkylethynyl group, the alkylamino group, and the alkylepoxy group is independently represented as R 1 R 2 ，R 2 Selected from vinyl, ethynyl, amino or epoxy groups; wherein R1 is selected from a direct bond, a C1-C10 linear or branched alkylene group, and carbon atoms and hydrogen atoms in the alkylene group are respectively and selectively replaced by S or O;
preferably, said R 1 Selected from direct bond, C1-C5 straight chain or branched chain alkylene.
3. The resin composition according to claim 1, wherein,
the nitrogen-containing six-membered heterocyclic compound is a compound shown in a formula (A), at least one of the Ra, the Rb and the Rc end groups is epoxy, and at least one of the Ra, the Rb and the Rc end groups is vinyl, ethynyl or allyl;
or, the nitrogen-containing six-membered heterocyclic compound is a compound shown in a formula (B), at least one of end groups of Rd, re and Rf is epoxy, and at least one of the end groups is vinyl, ethynyl or allyl;
or, the nitrogen-containing six-membered heterocyclic compound comprises a compound shown in the formula (A) and a compound shown in the formula (B), and the mass ratio of the compound shown in the formula (A) to the compound shown in the formula (B) is 1-49:1-49, preferably 1-9:9-1; wherein at least one of the terminal groups of Ra, rb, rc is vinyl, allyl, or ethynyl, preferably Ra, rb, rc are each independently vinyl, allyl, or ethynyl; at least one of the end groups of Rd, re and Rf is an epoxy group, and preferably the end groups of Rd, re and Rf are each independently an epoxy group.
4. The resin composition according to claim 1, wherein the nitrogen-containing six-membered heterocyclic compound is selected from at least one of the following formulas (a) to (d):
5. the resin composition according to any one of claims 1 to 4, wherein the alkali-soluble epoxy acrylic resin comprises at least one of a carboxylic acid-modified bisphenol a-type epoxy resin, a carboxylic acid-modified bisphenol F-type epoxy resin, a carboxylic acid-modified bisphenol S-type epoxy resin, and a carboxylic acid-modified novolac epoxy resin, and has an acid value of 50 to 100mg KOH/g and a solid content of 40 to 50wt%.
6. The resin composition according to any one of claims 1 to 4, wherein the photoinitiator is selected from at least one of a radical polymerization photoinitiator or a cationic polymerization photoinitiator;
preferably, the free radical polymerization photoinitiator is selected from at least one of benzoin and derivatives, alkyl benzene ketone compounds, acyl phosphine oxides, diphenyl ketone compounds and thioxanthone compounds;
preferably, the cationic polymerization photoinitiator is selected from at least one of diaryl iodonium salt, triaryliodonium salt, alkyl iodonium salt, isopropylbenzene ferrocene hexafluorophosphate.
7. The composition according to any one of claims 1 to 4, wherein the resin composition further comprises a thermosetting agent comprising at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, alicyclic type epoxy resin, and the thermosetting agent has an epoxy equivalent of 100 to 400g/eq.
8. The composition of any one of claims 1 to 4, wherein the resin composition further comprises an auxiliary agent comprising at least one of a toughening agent, a dispersing agent, a leveling agent, a defoaming agent, a colorant;
preferably, the amount of the toughening agent is 0 to 10 parts by mass;
preferably, the dispersant, the leveling agent, the defoamer, and the colorant are each independently used in an amount of 0 to 1 part by mass.
9. A photosensitive resist insulating film, characterized in that the material of the photosensitive resist insulating film is the photosensitive resist resin composition according to any one of claims 1 to 8.
10. An electronic component comprising the photosensitive solder resist insulating film according to claim 9 or a hardened film formed by curing the photosensitive solder resist insulating film according to claim 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311615350.4A CN117706870A (en) | 2023-11-29 | 2023-11-29 | Photosensitive solder resist resin composition, photosensitive solder resist insulating film and electronic component |
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| CN202311615350.4A CN117706870A (en) | 2023-11-29 | 2023-11-29 | Photosensitive solder resist resin composition, photosensitive solder resist insulating film and electronic component |
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| CN202311615350.4A Pending CN117706870A (en) | 2023-11-29 | 2023-11-29 | Photosensitive solder resist resin composition, photosensitive solder resist insulating film and electronic component |
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| Country | Link |
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| CN (1) | CN117706870A (en) |
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