CN114114837A - Dry film resist and preparation method thereof - Google Patents
Dry film resist and preparation method thereof Download PDFInfo
- Publication number
- CN114114837A CN114114837A CN202111415164.7A CN202111415164A CN114114837A CN 114114837 A CN114114837 A CN 114114837A CN 202111415164 A CN202111415164 A CN 202111415164A CN 114114837 A CN114114837 A CN 114114837A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- meth
- layer
- dry film
- resist layer
- 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
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 125
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 84
- -1 isooctyl Chemical group 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000011241 protective layer Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012965 benzophenone Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
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- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 claims description 7
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000654 additive Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 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 claims description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 4
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- SGSKTOKJZHJRCN-UHFFFAOYSA-N 4-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2 SGSKTOKJZHJRCN-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 claims description 3
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 claims description 3
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 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
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 3
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- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- FLQMMIWLCOMISX-UHFFFAOYSA-N 9-(2-methylphenyl)acridine Chemical compound CC1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 FLQMMIWLCOMISX-UHFFFAOYSA-N 0.000 claims description 3
- DOGGTYYFTFGYQM-UHFFFAOYSA-N 9-(3-methylphenyl)acridine Chemical compound CC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 DOGGTYYFTFGYQM-UHFFFAOYSA-N 0.000 claims description 3
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
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- ZABFSYBSTIHNAE-UHFFFAOYSA-N 1-(dimethylamino)butan-2-ol Chemical compound CCC(O)CN(C)C ZABFSYBSTIHNAE-UHFFFAOYSA-N 0.000 description 1
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- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
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- 229920002799 BoPET Polymers 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
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- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a dry film resist and a preparation method thereof. The dry film resist comprises a support layer and a resist layer, wherein the raw materials for forming the resist layer comprise alkali-soluble resin, photopolymerizable monomer and photoinitiator, and the dry film resist is characterized in that the resist layer is a pre-crosslinking layer, and the crosslinking degree of the resist layer is 2-15%. The resist layer is set as a pre-crosslinking layer, namely the resist layer is in a partially crosslinked structure before rolling, the fluidity of the resist layer after pre-crosslinking is effectively controlled, and the sufficient follow-up performance of the resist layer is ensured by controlling the crosslinking degree of the resist layer. Meanwhile, the resist layer with the crosslinking degree of 2-15% has sufficient resolution and developing property, and does not influence the use requirement of subsequent patterning.
Description
Technical Field
The invention relates to the technical field of corrosion resistance, in particular to a dry film corrosion inhibitor and a preparation method thereof.
Background
Dry film resists are widely used as key materials for pattern transfer in printed circuit boards, lead frames, solar cells, conductor packages, bga (ball Grid array), cps (chip Size package) packages. For example, in the production of a printed wiring board, a dry film resist is first bonded to a copper substrate, and the dry film resist is covered with a mask having a predetermined pattern, followed by pattern exposure or direct exposure by laser direct writing. Then, using weak alkaline aqueous solution as developing solution to remove unexposed part, then implementing etching or electroplating treatment to form pattern, finally stripping off by remover to remove dry film solidified part so as to implement pattern transfer.
Dry film resists are generally composed of a three-layer structure of a support film (PET), a resist layer, and a cover film (PE), and are generally sold in the form of a dry film roll. The components of the intermediate resist layer mainly include alkali-soluble resin, photopolymerizable monomer, photoinitiator, auxiliary agent, and the like. Therefore, when the dry film is transported and stored in a roll form, the middle resist layer has certain fluidity under the action of pressure, namely the resist layer partially flows to cause uneven thickness and overflows to two ends of the dry film roll to generate gummosis (or gummosis), so that the normal use of the dry film is influenced, the quality guarantee period of the dry film is shortened, and the quality guarantee period of the cut dry film roll in the current market can only be kept about 1-3 months generally.
In the patent application CN108227379A, cellulose is added to increase the viscosity of the photopolymerizable component to improve the flow, and a proper amount of plasticizer is added to adjust the viscosity of the photopolymerizable component to maintain the flexibility and adhesion of the dry film. In patent publication No. CN101196686B, by adjusting the synthetic composition of the alkali-soluble resin, a dry film resist is provided which has good resolution after development, reduced generation of aggregates, and good bleeding and follow-up properties.
Disclosure of Invention
The invention mainly aims to provide a dry film resist and a preparation method thereof, and aims to solve the problem that a resist layer in the dry film resist in the prior art is easy to flow.
In order to achieve the above object, according to one aspect of the present invention, there is provided a dry film resist comprising a support layer and a resist layer, raw materials for forming the resist layer comprising an alkali-soluble resin, a photopolymerizable monomer and a photoinitiator, characterized in that the resist layer is a pre-crosslinked layer, and the degree of crosslinking of the resist layer is 2% to 15%.
Further, the degree of crosslinking of the resist layer is 3% to 10%; the acid value of the alkali-soluble resin is preferably in the range of 90 to 200mg KOH/g.
Further, the weight average molecular weight of the alkali-soluble resin is 50000-200000, preferably 70000-150000.
Further, the above alkali-soluble resin is obtained by copolymerizing one or more carboxyl group-containing first copolymerized unit monomers with one or more second copolymerized unit monomers having no carboxyl group, the second copolymerized unit monomers being selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, poly (meth), Ethyl N, N-dimethyl (meth) acrylate, ethyl N, N-diethyl (meth) acrylate, propyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl N, N-dimethyl (meth) acrylate, butyl N, N-diethyl (meth) acrylate, (meth) acrylamide, N-hydroxymethyl-acrylamide, N-butoxymethyl-acrylamide, styrene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (alkoxylated) nonylphenol (meth) acrylate, preferably the first comonomer is selected from itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, and, Any one or more of vinyl acetic acid and anhydride thereof.
Further, the photopolymerizable monomer is selected from any one or more of lauryl acrylate, isodecyl acrylate, tetrahydrofuryl acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene (propylene) glycol diacrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate.
Further, the photoinitiator is selected from one or a combination of more of benzoin ether, benzophenone and derivatives thereof, thioxanthone compounds, anthraquinone and derivatives thereof, thioxanthone compounds, hexaarylbisimidazole compounds and acridine compounds according to any ratio, and the photoinitiator is preferably selected from benzoin ether, benzophenone, thioxanthone, anthraquinone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, 2-methylanthraquinone, and the like, Benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzoin dimethyl methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, benzophenone, 4 ' -bis (dimethylamino) benzophenone (michelson), 4 ' -bis (diethylamino) benzophenone, isopropylthioxanthone, 2-chlorothianthrone, 2, 4-diethylthioxanthone, 2-tert-butylanthraquinone, ethyl N, N-dimethylbenzoate, dimethylaminoethyl benzoate, N-dimethylethanolamine, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, any one of 2 ' -diimidazole, 2 ' -bis (2-bromo-5-methoxybenzene) -4,4 ', 5,5 ' -tetraphenyldiimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, 9-phenylacridine, 9-p-phenylacridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-chlorophenylacridine, and 1, 7-bis (9-acridinyl) heptane.
Further, the raw materials for forming the resist layer comprise, by weight, 40-60 parts of alkali-soluble resin, 35-60 parts of photopolymerizable monomer and 1-5 parts of photoinitiator, and preferably, the raw materials for forming the resist layer comprise, by weight, 40-60 parts of alkali-soluble resin, 38-58 parts of photopolymerizable monomer and 1-3 parts of photoinitiator; preferably, the raw materials also comprise 1-5 parts by weight of additives.
Further, the dry film resist further comprises a protective layer, and the supporting layer, the resist layer and the protective layer are sequentially arranged.
According to another aspect of the present invention, there is provided a method of preparing the dry film resist of any one of the above, the method comprising: dispersing raw materials including alkali-soluble resin, a photopolymerizable monomer and a photoinitiator in an organic solvent to form a mixture with the solid content of 30-55%, wherein the organic solvent is preferably one or more selected from methanol, ethanol, n-butanol, isopropanol, acetone, butanone, propylene glycol methyl ether, toluene and xylene; arranging the mixture on the supporting layer to form a coating, and drying the coating to obtain a resist layer preparation layer; carrying out ultraviolet irradiation pre-crosslinking or radiation pre-crosslinking treatment on the resist layer preparation layer to obtain a resist layer; and (6) rolling.
Further, the light source of the ultraviolet irradiation pre-crosslinking is an ultraviolet lamp with the wavelength of 200-410 nm, and the ultraviolet lamp is a high-pressure mercury lamp or a UV-LED lamp.
Further, the irradiation pre-crosslinking described above is realized by an excimer laser or a semiconductor laser.
Further, the energy of the ultraviolet radiation pre-crosslinking is 0.1-20 mJ/cm2。
Further, before pre-crosslinking the resist layer preparation layer, the preparation method further comprises: a protective layer is provided on the resist layer preparation layer.
By applying the technical scheme of the invention, the resist layer is set as the pre-crosslinking layer, namely the resist layer is in a partially crosslinked structure before rolling, the fluidity of the resist layer after pre-crosslinking is effectively controlled, and the sufficient follow-up performance of the resist layer is ensured by controlling the crosslinking degree of the resist layer. Meanwhile, the resist layer with the crosslinking degree of 2-15% has sufficient resolution and developing property, and does not influence the use requirement of subsequent patterning.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the present application, when the dry film in the prior art is transported and stored in a roll form, the middle resist layer has a certain fluidity under the action of pressure, that is, the resist layer partially flows to cause uneven thickness, and overflows to both ends of the dry film roll, that is, glue flow (or glue overflow) is generated, thereby affecting the normal use of the dry film and shortening the shelf life thereof. It can be seen that the resist layer is subjected to a glue flow phenomenon due to the fact that the resist layer is squeezed after being rolled, and thus the fluidity of the resist layer needs to be reduced before being rolled, but in the application of the dry film resist, the resist layer also needs to have certain followability so as to be capable of automatically filling up the surface unevenness of an object to be patterned, and the conventional solution at present is to design an alkali-soluble resin for forming the resist layer, for example, the technology adopted in the patent with the publication number of CN 101196686B. However, this method is technically difficult and costly. The present application has studied the influence of the flow property and the following property on the developing effect, and has found that the lamination pressure is much greater than the pressure inside the roll when the resist layer is used, so that the following property can be satisfied even if the flow property is reduced by a certain reduction of the following property, wherein the factors influencing the flow property directly influence the flow property by the crosslinking degree in addition to the characteristics of the alkali soluble resin.
In an exemplary embodiment of the present application, a dry film resist is provided, the dry film resist including a support layer and a resist layer, raw materials for forming the resist layer including an alkali-soluble resin, a photopolymerizable monomer and a photoinitiator, the resist layer being a pre-crosslinked layer, and a crosslinking degree of the resist layer being 2% to 15%.
According to the application, the corrosion-resistant layer is set to be the pre-crosslinking layer, namely the corrosion-resistant layer is in a partially crosslinked structure before rolling, the fluidity of the corrosion-resistant layer after pre-crosslinking is effectively controlled, and the sufficient follow-up performance of the corrosion-resistant layer is ensured by controlling the crosslinking degree of the corrosion-resistant layer. Meanwhile, the resist layer with the crosslinking degree of 2-15% has sufficient resolution and developing property, and does not influence the use requirement of subsequent patterning.
Further, the degree of crosslinking of the resist layer is preferably 3% to 10% in order to further control the fluidity of the resist layer and improve the follow-up property.
Because the resist layer is crosslinked to a certain degree, in order to ensure the efficiency and the adhesion of subsequent development, the acid value of the alkali-soluble resin is preferably in a range of 90-200 mg KOH/g, when the acid value is lower than 90mg KOH/g, the development difficulty is high, and a pattern with good appearance is difficult to obtain under the conventional development condition; when the acid value exceeds 200mgKOH/g, pattern peeling is likely to occur during development, resulting in development defects.
In order to further control the fluidity of the resist layer and to improve the adhesion of the pattern obtained after development as much as possible, the weight average molecular weight of the alkali-soluble resin is preferably 50000 to 200000, and preferably 70000 to 150000. When the weight average molecular weight is greater than 200000, the flatness of the resist layer after exposure and development is reduced, and the resolution is reduced; when the weight average molecular weight is less than 50000, the development operation window may become narrow, and the adhesion of the developed pattern to the substrate may be reduced.
The alkali-soluble resin used in the present application may be selected from alkali-soluble resins conventionally used in the art, and in order to control the cost of the alkali-soluble resin, it is preferred that the alkali-soluble resin is copolymerized from one or more carboxyl group-containing first copolymerized unit monomers and one or more carboxyl group-free second copolymerized unit monomers selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, or vinyl acetate, and vinyl acetate, and the like, vinyl acetate, and the like, and the, Any one or more of polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, ethyl N, N-dimethyl (meth) acrylate, ethyl N, N-diethyl (meth) acrylate, propyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl N, N-dimethyl (meth) acrylate, butyl N, N-diethyl (meth) acrylate, (meth) acrylamide, N-methylol-acrylamide, N-butoxymethyl-acrylamide, styrene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (alkoxylated) nonylphenol (meth) acrylate, preferably, the first comonomer unit monomer is selected from any one or more of itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, vinyl acetic acid and anhydrides thereof.
The photopolymerizable monomers used in the present application may also be selected from photopolymerizable monomers that are conventional in the art, and in order to be more easily cross-linked with the alkali soluble resin, it is preferred that the photopolymerizable monomers are selected from any one or more of lauryl acrylate, isodecyl acrylate, tetrahydrofuryl acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene (propylene) glycol diacrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate.
The photoinitiator used in the present application can also be selected from the photoinitiators commonly used in the art, for example, the photoinitiator is selected from one or more of benzoin ether, benzophenone and derivatives thereof, thioxanthone compounds, anthraquinone and derivatives thereof, thioxanthone compounds, hexaarylbisimidazole compounds, acridine compounds in any ratio, and the photoinitiator is preferably selected from benzoin ether, benzophenone, thioxanthone, anthraquinone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, etc, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzoin dimethyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, benzophenone, 4 '-bis (dimethylamino) benzophenone (mikrolone), 4' -bis (diethylamino) benzophenone, isopropylthioxanthone, 2-chlorothianthrone, 2, 4-diethylthioxanthone, 2-tert-butylanthraquinone, ethyl N, N-dimethylbenzoate, dimethylaminoethyl benzoate, N-dimethylethanolamine, N-dimethylethanolamine, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin dimethyl ketal, benzoin methyl ketal, 4-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-tert-butylanthracene, ethyl N, N-dimethylethanolamine, N-methyl benzoate, N-methyl ketal, and N-methyl ketal, 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -diimidazole, 2 '-bis (2-bromo-5-methoxybenzene) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole, 9-phenylacridine, 9-p-phenylacridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-chlorophenylacridine, 1, 7-bis (9-acridinyl) heptane.
In order to further balance the flow property, the follow-up property and the developing property, the raw materials for forming the resist layer preferably comprise 40 to 60 parts by weight of alkali-soluble resin, 35 to 60 parts by weight of photopolymerizable monomer and 1 to 5 parts by weight of photoinitiator. Preferably, the raw materials for forming the resist layer comprise, by weight, 40-60 parts of an alkali-soluble resin, 38-58 parts of a photopolymerizable monomer and 1-3 parts of a photoinitiator.
The dry film resist of the present invention may further include an additive, for example, 1 to 5 parts by weight of an additive, such as a dye, a photo-coupler, a color-forming heat stabilizer, a plasticizer, a pigment, a filler, an antifoaming agent, a flame retardant, a stabilizer, a leveling agent, a peeling promoter, an antioxidant, a perfume, an imaging agent, and other auxiliaries.
The fluidity of the resist layer formed after pre-crosslinking is greatly reduced, and during coiling, a release agent can be arranged on the back surface (the surface of the side without the resist layer) of the supporting layer, and then coiling is carried out, so that the back surface of the supporting layer and the resist layer can be favorably stripped. Of course, the skilled person can choose whether to set the protective layer according to the storage time and transportation requirement of the dry film resist, for example, when the storage time is long or the transportation requirement is long, which results in a high probability of damage to the resist layer, it is preferable that the dry film resist further comprises a protective layer, and the support layer, the resist layer and the protective layer are sequentially set. On one hand, the resist layer is protected, on the other hand, the adhesion between the resist layer and the back surface of the supporting layer is avoided, and the back surface of the supporting layer and the resist layer are favorably stripped during roll breaking.
In another exemplary embodiment of the present application, there is provided a method of preparing a dry film resist of any one of the above, including: dispersing raw materials including alkali-soluble resin, photopolymerizable monomer and photoinitiator in an organic solvent to form a mixture with a solid content of 30-55%; arranging the mixture on the supporting layer to form a coating, and drying the coating to obtain a resist layer preparation layer; and carrying out ultraviolet radiation pre-crosslinking or radiation pre-crosslinking treatment on the resist layer preparation layer to obtain a resist layer, and rolling.
After the resist layer preparation layer is arranged and before the rolling, the resist layer preparation layer is subjected to pre-crosslinking treatment, so that the flow property of the resist layer preparation layer is effectively controlled. The skilled person can adjust the pre-crosslinking conditions to control the degree of crosslinking between 2% and 15%.
The organic solvent used for dispersing the alkali-soluble resin, the photopolymerizable monomer and the photoinitiator may be selected from organic solvents having good dissolving ability for the above components, and in order to ensure the drying treatment efficiency of the thickness, it is preferable that the fir organic solvent is selected from one or more of methanol, ethanol, n-butanol, isopropanol, acetone, butanone, propylene glycol methyl ether, toluene and xylene.
Preferably, when the dry film resist includes a protective layer, the resist layer preparation layer may be pre-crosslinked first and then the protective layer may be disposed on the resist layer, or the protective layer may be disposed first and then pre-crosslinked. Preferably, before the pre-crosslinking of the resist layer preparation layer, the above preparation method further comprises: a protective layer is provided on the resist layer preparation layer. Preferably, after the protective layer is provided, the resist layer preparation layer is irradiated from the support layer side.
The pre-crosslinking mode of the present application can be achieved by ultraviolet irradiation or laser irradiation. Ultraviolet lamps with the wavelength range of 200-410 nm can be selected for ultraviolet irradiation, such as high-pressure mercury lamps and UV-LED lamps; laser irradiation may be achieved by excimer lasers, or semiconductor lasers. Such as a KrF excimer laser, Ar ion laser, YAG laser, or the like.
In some embodiments, the energy of the ultraviolet irradiation pre-crosslinking is selected from 0.1-20 mJ/cm2The energy of the ultraviolet light is further selected within the above range so that the degree of pre-crosslinking falls within the range of 2% to 15%, further within the range of 3% to 10% crosslinking degree, depending on the dry film sensitivity used.
When the dry film resist is used, the dry film resist is usually adhered to a printed circuit board and then exposed and cured, in the process, for example, a UV exposure machine is used, a buffer 41-step exposure ruler is used, and the exposure energy is 30-60 mJ/cm under the normal working grid number of 20-23 grids2The dry film resist laminate obtained by exposure is a common dry film resist laminate, and the exposure energy is 3-15 mJ/cm2The dry film resist laminate obtained by exposure is a high-sensitivity dry film resist laminate, a semi-high-sensitivity dry film resist laminate between the normal dry film resist laminate and the high-sensitivity dry film resist laminate, and the required energy is 15-30 mJ/cm2。
Correspondingly, when the dry film resist is used as a raw material of a common dry film resist laminated body, the energy of the pre-crosslinking treatment is 1-18 mJ/cm2More preferably 2 to 10mJ/cm2(ii) a When the dry film resist is used as a raw material of a highly sensitive dry film resist laminate, the energy of the pre-crosslinking treatment is 0.1 to 2mJ/cm2More preferably 0.1 to 1mJ/cm2(ii) a When the dry film resist is used as a raw material of a semi-highly sensitive dry film resist laminate, the energy of the pre-crosslinking treatment is 0.3 to 7mJ/cm2More preferably 0.5 to 3mJ/cm2。
If the energy of the pre-crosslinking treatment is too low, the pre-crosslinking degree of the resist layer is low, and the control capability on the risk of the adhesive is weak; if the energy of the pre-crosslinking treatment is too high, the pre-crosslinking degree of the resist layer is high, which causes exposure risk, poor flexibility of the dry film, reduced followability, and reduced resolution and adhesiveness after exposure and development.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The alkali soluble resin was prepared by the following procedure: uniformly mixing methacrylic acid MAA, methyl methacrylate MMA, butyl acrylate BA and styrene ST according to the mass ratio of table 1 to form a mixed solution, adding initiators of azobisisobutyronitrile AIBN and butanone, stirring and dissolving, adding about 35% of the mixed solution in mass fraction into a three-neck flask protected by nitrogen and provided with a condensation reflux device through a peristaltic pump, heating to 80 ℃ in an oil bath, stirring and reacting for 1h, slowly dropwise adding the rest of the mixed solution, and finishing the addition within 3 h. And after continuing the heat preservation reaction for 4 hours, heating to 90 ℃, supplementing butanone solution for dissolving a small amount of initiator twice at an interval of 1 hour, preserving heat and stirring for 3 hours after the dropwise addition is finished, and finishing the reaction to obtain the alkali-soluble copolymer resin.
Different alkali soluble copolymer resins A-1, A-2 and A-3 are obtained according to different mass ratios of MAA, MMA, BA and ST, and corresponding dry resins (the dry resins are resins with solvent removed) with different properties are shown in Table 1.
TABLE 1
2. Preparation of dry film resist:
and mixing a photopolymerizable monomer, a photoinitiator and an additive into an alkali-soluble resin solution, adding a certain amount of solvent to prepare a mixture with solid content of 40%, stirring at room temperature for 4 hours to completely dissolve, and removing impurities by using a 200-mesh filter to obtain a resist layer glue solution.
And uniformly coating the resist layer glue solution on a PET film (with the thickness of 16-18 microns) by using a coating machine, setting the temperature of an oven to be 95 ℃, drying for 5-12 min to form a resist preparation layer, and covering a PE film (with the thickness of 18-22 microns) on the resist preparation layer. Different thicknesses of the resist preparation layer can be obtained by selecting different wire rods, and the thickness of the dried resist preparation layer is 30 μm or 38 μm. The resist composition is shown in table 2 below.
TABLE 2
Note: photopolymerizable monomers used in the examples and comparative examples of the present application:
b-1 (10) ethoxylated bisphenol A diacrylate (Miwon Specialty Chemical, M2101).
B-2 (9) ethoxylated trimethylolpropane triacrylate (Sadoma, USA, SR502 NS).
B-3: (2) ethoxy (7) propoxynonylphenol acrylate (Han agricultural chemical, NPF-721).
Photoinitiators used in the examples and comparative examples of the present application:
c-1: 2,2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole (Changzhou strong electron material).
C-2: 4, 4' -bis (diethylamino) benzophenone (a Changzhou powerful electronic material).
C-3: n-phenylglycine (Western Asia chemical).
Auxiliary agent:
d-1: diamond green (Shanghai ladder love chemical industry).
D-2: leuco crystal violet (Shanghai ladder love chemical industry).
[ Cross-linking degree test ]
And setting a pre-crosslinking illumination parameter, namely illumination energy by adopting a Photo-DSC method.
Degree of precrosslinking ═ area of exothermic peak of uncrosslinked sample-area of exothermic peak of precrosslinked sample)/area of exothermic peak of uncrosslinked sample
[ Exposure ] to light
And carrying out exposure in 365nm and 385nm wave bands by adopting a Hongsheng Xiang LED exposure machine.
[ DEVELOPING ]
And developing the exposed sample by using a sodium carbonate aqueous solution with the mass concentration of 1% at the temperature of 30 ℃, wherein the developing pressure is 1.5bar, and the developing time is 2 times of the shortest developing time. And drying the test substrate at 50 ℃ after the development is finished.
[ evaluation of resolution ]
The exposure was performed using a mask having a wiring pattern with a width of 1:1 of the exposed portion and the unexposed portion, and after development with 1.5 times the minimum development time, the minimum mask width where the cured resist line was normally formed was taken as the value of the resolution.
[ evaluation of adhesion force ]
A photosensitive dry film resist was laminated on a copper plate by hot-pressing a film, exposed to light using a mask having a wiring pattern with a width of n:400 of an exposed portion and an unexposed portion, and developed with 2 times of the minimum development time, and then the minimum mask width where a cured resist line was normally formed was taken as a value of adhesion.
[ evaluation of storage stability ]
After the dry film is prepared, the dry film is cut into pieces with the width of 248mm and the length of 200m, the pieces are wound into a roll under fixed tension, the roll is placed in a constant temperature and humidity box with the temperature of 20 ℃ and the RH of 60 percent, and the glue overflow condition at the two ends is checked regularly. And (5) timing from the time of placing the glue in the glue container until glue overflows from two ends, and recording the total time length.
[ evaluation of filling Property ]
Preparing a filling substrate: and cutting a proper dry film resist laminated body sample according to the size of the copper-clad plate, pasting the cut dry film resist laminated body with a film, and standing for 15 minutes in a backlight mode. Then, a film having a pit shape to be formed is selected, and exposure (exposure scale with exposure grid number of 20 to 23 ST/41) and development are performed. And (3) pretreating and microetching, namely thinning copper by microetching to obtain pits, thinning the copper by 0.5-1.5 mu m once, and controlling the depth of the pits by controlling the microetching frequency, wherein the common depth range is 6-15 mu m. And (4) removing the film, namely soaking the film in 3% sodium hydroxide for removing the film, and then washing and drying the film. And (4) thickness testing, namely testing the thickness of copper plating, namely pit depth, by using a surface roughness meter.
Preparation of filling sample: cutting a dry film resist laminated body sample according to the size of a copper-clad plate, pasting a film, exposing, developing, finally observing the filling condition of the dry film by using a scanning electron microscope SEM, selecting a linear pit with a line width and a line distance of 3mil, and if the dry film can completely fill the pit with the depth of 8 mu m (no gap at the corner) but can not fill the pit with the depth of 10 mu m, indicating that the filling capacity of the dry film is 8 mu m.
The results of the measurements are reported in table 3.
TABLE 3
As can be seen from the above table, compared with comparative example 1, the glue overflow rate of examples 1-11 after pre-crosslinking treatment is significantly reduced, the storage stability is significantly improved, and in addition, the dry film has no significant negative effect on the filling performance. In example 1, the resin molecular weight was too high, resulting in poor analysis, and in example 2, the resin molecular weight was too low, resulting in poor adhesion. In examples 7 and 9, since the dry film thickness was 30 μm, the filling performance was weaker as the film thickness was thinner, and thus, the filling performance was slightly lower in both examples 7 and 9. From example 11, it is clear that, although the flash rate can be reduced to the same extent and the storage stability can be improved by pre-crosslinking from the side of the protective film PE, the follow-up property of the dry film is affected to a certain extent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement 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 dry film resist comprises a support layer and a resist layer, wherein raw materials for forming the resist layer comprise alkali-soluble resin, a photopolymerizable monomer and a photoinitiator, and the dry film resist is characterized in that the resist layer is a pre-crosslinking layer, and the crosslinking degree of the resist layer is 2-15%.
2. The dry film resist according to claim 1, wherein the degree of crosslinking of the resist layer is 3% to 10%; the acid value of the alkali-soluble resin is preferably in the range of 90-200 mg KOH/g.
3. The dry film resist according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 50000 to 200000, preferably 70000 to 150000.
4. The dry film resist of claim 1, wherein the alkali soluble resin is copolymerized from one or more first copolymerized unit monomers containing carboxyl groups and one or more second copolymerized unit monomers not containing carboxyl groups, the second copolymerized unit monomers being selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (meth) acrylate), poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, poly (2 (acrylate, poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, poly (2-acrylate, poly (acrylate, and poly (acrylate, poly (meth) acrylate, poly (acrylate), poly (acrylate, poly (meth) acrylate), poly (acrylate), poly (acrylate, poly (, (meth) acrylonitrile, glycidyl (meth) acrylate, ethyl N, N-dimethyl (meth) acrylate, ethyl N, N-diethyl (meth) acrylate, propyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl N, N-dimethyl (meth) acrylate, butyl N, N-diethyl (meth) acrylate, (meth) acrylamide, N-methylol-acrylamide, N-butoxymethyl-acrylamide, styrene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (alkoxylated) nonylphenol (meth) acrylate, preferably the first comonomer is selected from any one or more of itaconic acid, crotonic acid, acrylic acid, methacrylic acid, acrylic acid, or a methacrylic acid, acrylic acid, or a derivative thereof, or a, Any one or more of methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, vinyl acetic acid and anhydride thereof.
5. The dry film resist of claim 1, wherein the photopolymerizable monomer is selected from any one or more of lauryl acrylate, isodecyl acrylate, tetrahydrofuryl acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene (propylene) glycol diacrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate.
6. The dry film resist according to claim 1, wherein the photoinitiator is selected from the group consisting of one or more of benzoin ethers, benzophenones and derivatives thereof, thioxanthone compounds, anthraquinones and derivatives thereof, thioxanthone compounds, hexaarylbisimidazoles, acridine compounds in any ratio, preferably the photoinitiator is selected from the group consisting of benzoin ethers, benzophenones, thioxanthone, anthraquinones, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzoin bismethyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, benzophenone, 4 '-bis (dimethylamino) benzophenone (mikimone), 4' -bis (diethylamino) benzophenone, isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-tert-butylanthraquinone, ethyl N, N-dimethylbenzoate, dimethylaminoethyl benzoate, N-dimethylethanolamine, 2, any one of 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -diimidazole, 2 '-bis (2-bromo-5-methoxybenzene) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole, 9-phenylacridine, 9-p-phenylacridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-chlorophenylacridine, 1, 7-bis (9-acridinyl) heptane.
7. The dry film resist according to claim 1, wherein the resist layer is formed from the raw materials comprising, by weight, 40 to 60 parts of the alkali-soluble resin, 35 to 60 parts of the photopolymerizable monomer, and 1 to 5 parts of the photoinitiator, preferably from 40 to 60 parts of the alkali-soluble resin, 38 to 58 parts of the photopolymerizable monomer, and 1 to 3 parts of the photoinitiator; preferably, the raw materials further comprise 1-5 parts by weight of additives.
8. The dry film resist according to claim 1, further comprising a protective layer, wherein the support layer, the resist layer and the protective layer are disposed in this order.
9. The method of preparing a dry film resist according to any one of claims 1 to 8, comprising:
dispersing raw materials including alkali-soluble resin, photopolymerizable monomer and photoinitiator in an organic solvent to form a mixture with a solid content of 30-55%, wherein the organic solvent is preferably selected from one or more of methanol, ethanol, n-butanol, isopropanol, acetone, butanone, propylene glycol methyl ether, toluene and xylene;
arranging the mixture on a support layer to form a coating, and drying the coating to obtain a resist layer preparation layer;
carrying out ultraviolet radiation pre-crosslinking or radiation pre-crosslinking treatment on the resist layer preparation layer to obtain the resist layer, rolling,
preferably, the light source of the ultraviolet radiation pre-crosslinking is an ultraviolet lamp with the wavelength of 200-410 nm, the ultraviolet lamp is a high-pressure mercury lamp or a UV-LED lamp,
preferably, the irradiation pre-crosslinking is effected by an excimer laser or a semiconductor laser,
further preferably, the energy of the pre-crosslinking is 0.1-20 mJ/cm2。
10. The production method according to claim 9, characterized in that, before the pre-crosslinking the resist layer preparation layer, the production method further comprises: and arranging a protective layer on the resist layer preparation layer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875322A (en) * | 2003-11-25 | 2006-12-06 | 东京应化工业株式会社 | Chemically amplified positive photosensitive thermosetting resin composition, method of forming cured article, and method of producing functional device |
| KR20080003949A (en) * | 2006-07-04 | 2008-01-09 | 주식회사 코오롱 | Dry film photoresist |
| CN105511227A (en) * | 2015-12-26 | 2016-04-20 | 杭州福斯特光伏材料股份有限公司 | Dry film resist with good hole shielding function and laminated body thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875322A (en) * | 2003-11-25 | 2006-12-06 | 东京应化工业株式会社 | Chemically amplified positive photosensitive thermosetting resin composition, method of forming cured article, and method of producing functional device |
| KR20080003949A (en) * | 2006-07-04 | 2008-01-09 | 주식회사 코오롱 | Dry film photoresist |
| CN105511227A (en) * | 2015-12-26 | 2016-04-20 | 杭州福斯特光伏材料股份有限公司 | Dry film resist with good hole shielding function and laminated body thereof |
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