CN118068647A - Water-based LED-UV (light-emitting diode-ultraviolet) anti-etching electroplating photosensitive adhesive - Google Patents
Water-based LED-UV (light-emitting diode-ultraviolet) anti-etching electroplating photosensitive adhesive Download PDFInfo
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- CN118068647A CN118068647A CN202410308810.7A CN202410308810A CN118068647A CN 118068647 A CN118068647 A CN 118068647A CN 202410308810 A CN202410308810 A CN 202410308810A CN 118068647 A CN118068647 A CN 118068647A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000005530 etching Methods 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 239000000853 adhesive Substances 0.000 title claims abstract description 29
- 238000009713 electroplating Methods 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 24
- -1 acrylic ester Chemical class 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 239000013008 thixotropic agent Substances 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000003504 photosensitizing agent Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 8
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- UQRKXZOISAAYQQ-UHFFFAOYSA-N diphenylphosphorylformaldehyde Chemical compound C=1C=CC=CC=1P(=O)(C=O)C1=CC=CC=C1 UQRKXZOISAAYQQ-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007747 plating Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the technical field of polymers, in particular to an aqueous LED-UV (light-emitting diode-ultraviolet) anti-etching electroplating photosensitive adhesive. The invention provides a water-soluble photosensitive resin and a preparation method thereof. The water-soluble photosensitive resin is mainly prepared from phenolic epoxy resin, and the resin coating has high hardness, strong impact resistance, heat resistance and good chemical reagent resistance after being cured. The epoxy resin is added, has strong adhesiveness to a metal substrate, and has good heat resistance and chemical resistance due to C-C bond and ether bond in the polymer chain of the epoxy resin. The epoxy group and the hydroxyl in the epoxy resin can be used as reaction points to be connected into the acrylic ester monomer, so that the acrylic ester monomer has photo-curing activity, and the introduction of the carboxyl further increases the molecular weight of the resin, so that the heat resistance and the chemical solvent resistance are further improved. The anti-corrosion photoresist prepared by the invention has the characteristics of strong water solubility, high resolution, good heat resistance, high film stripping speed, good acid resistance and the like.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to an aqueous LED-UV (light-emitting diode-ultraviolet) anti-etching electroplating photosensitive adhesive.
Background
The photosensitive imaging etching resist has low viscosity and high reactivity, is widely applied in the field of liquid photosensitive imaging resist in recent years, and the solvents in the components of the photosensitive imaging etching resist are mostly organic solvents at present, so that the volatilization of VOC seriously affects the environmental pollution, and the development of the liquid photosensitive etching resist process from organic solvents to aqueous solvents has become a necessary trend for reducing the influence of the organic solvents on the environment. The anti-corrosion photoresist curing system is easy to volatilize, has high inflammable smell, is unsafe in use, can pollute the surrounding environment and can cause injury to users. Thus, a resist is prepared to overcome the above drawbacks, and it becomes important in the field of photo-curing systems.
In order to solve the problems, the invention provides the aqueous LED-UV anti-etching electroplating photosensitive adhesive, which overcomes the defects of easy volatilization, high flammable smell and the like of the traditional anti-etching curing system.
Disclosure of Invention
The invention aims to provide an aqueous LED-UV etching-resistant electroplating photosensitive adhesive for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the water-based LED-UV anti-etching electroplating photosensitive adhesive comprises the following raw materials in parts by weight:
30-35 parts of water-soluble photosensitive resin, 8-20 parts of water-based acrylic photosensitive monomer, 8-10 parts of water-based epoxy resin, 0.5-2 parts of photosensitizer, 3-6 parts of photoinitiator, 0.3-2 parts of pigment, 5-16 parts of filler, 1 part of dispersing agent, 0.25-0.5 part of defoaming agent, 8-10 parts of water, 0.6-1.2 parts of thixotropic agent, 0.2-0.5 part of wetting agent, 0.5 part of leveling agent, 1 part of multifunctional agent and 5 parts of film forming auxiliary agent;
The water-soluble photosensitive resin comprises the following raw materials in parts by weight:
31 parts of phenolic epoxy resin, 25-40 parts of polyfunctional acrylate monomer, 3-5 parts of dimethylol butyric acid, 65-90 parts of acrylic acid, 0.3-0.7 part of catalyst triphenylphosphine, 0.2-0.75 part of polymerization inhibitor p-methoxyphenol or p-hydroxyanisole, 9-18 parts of organic base or organic amine, 98-147 parts of maleic anhydride or 192-230 parts of metabenzoic anhydride, 7-8 parts of diethylene glycol monomethyl ether, 7-8 parts of diethylene glycol diethyl ether acetate and 56-64 parts of distilled water.
More preferably, the aqueous acrylic photosensitive monomer is any one or more of difunctional acrylic ester, trifunctional acrylic ester and hexafunctional acrylic ester.
More preferably, the photosensitizer is any one or more of benzophenone, 1173 and organophosphorus photosensitizers.
More preferably, the photoinitiator is any one or more of thioxanthone initiator ITX, diaryl phosphine oxide initiator TPO, UV-318 initiator, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethyl formyl-diphenyl phosphorus oxide.
More preferably, the pigment is any one or more of phthalocyanine blue, ferric oxide blue and ferric green.
More preferably, the filler is any one or more of calcium carbonate, talcum powder, silicon dioxide and transparent powder.
More preferably, the defoamer is polysiloxane DYK-280; the wetting agent is a biscytidine siloxane surfactant; the dispersing agent is any one or more of amino acrylic ester copolymer, phosphate and polybasic acid homopolymer; the thixotropic agent is bentonite.
More preferably, the preparation method of the water-soluble photosensitive resin comprises the following steps:
S1: uniformly mixing water-based novolac epoxy resin, acrylate monomer and dimethylolbutyric acid, heating to 75-90 ℃, then slowly dropwise adding acrylic acid, triphenylphosphine serving as a catalyst and p-hydroxyanisole serving as a polymerization inhibitor, heating to 105-110 ℃ and reacting for 6-8 hours to obtain novolac epoxy acrylate resin;
S2: adding the phenolic epoxy acrylate into the polymerization inhibitor para-hydroxyanisole and 0.1-0.2 part of catalyst triphenylphosphine again, fully and uniformly stirring, adding anhydride or phthalic anhydride, heating to 105-115 ℃, reacting for 8 hours, and controlling the acid value between 68-72;
s3: adding polymerization inhibitor, cooling, adding organic base or organic amine while stirring when the temperature is reduced to 40-50 ℃, and neutralizing until the pH value is 8-10; dropwise adding diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water mixed solvent under stirring to obtain water-based pale yellow transparent epoxy acrylic resin;
more optimally, the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps: and uniformly mixing water-soluble photosensitive resin, water-based acrylic acid photosensitive monomer, water-based epoxy resin, acrylic ester, photosensitizer, photoinitiator, pigment, filler, wetting agent, dispersing agent, defoaming agent, water and thixotropic agent, and grinding to the fineness of 1-5 um to obtain the anti-etching electroplating photosensitive adhesive.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a water-soluble photosensitive resin and a preparation method thereof. The water-soluble photosensitive resin is mainly prepared from phenolic epoxy resin, has high Tg value, and has the characteristics of high hardness, strong shock resistance, good heat resistance, good chemical reagent resistance and the like after being cured.
The invention adds epoxy resin. The hydroxyl on the molecular chain of the epoxy resin is a strong polar group, the epoxy resin has strong adhesion to a metal substrate, and the C-C bond and ether bond in the polymer chain of the epoxy resin enable the epoxy resin to have good heat resistance and chemical resistance. The epoxy acrylate has good insulativity, water resistance, heat resistance and solvent resistance after being cured.
The epoxy group and the hydroxyl in the aqueous epoxy resin can be used as reaction points to be connected into the acrylic ester monomer, so that the aqueous epoxy resin has photo-curing activity. In addition to obtaining hydrophilic groups, the introduction of carboxyl groups further increases the molecular weight of the resin, so that the heat resistance and chemical solvent resistance are further improved. In order to increase the water solubility, the carboxyl can be neutralized by amine to prepare ammonium salt, and the heat resistance and chemical solvent resistance of the generated ammonium salt are further enhanced.
The epoxy group on the epoxy resin and carboxyl in acrylic ester undergo ring-opening reaction to introduce a photosensitive group C=C double bond, so that the water-soluble photosensitive resin UV/EA is prepared. Hydroxyl generated by epoxy ring opening reaction in UV/EA reacts with maleic anhydride to generate hydrophilic photosensitive oligomer UV/EB containing carboxyl. To increase the water solubility, the carboxyl groups in the UV/EB are neutralized with alkali to form salt polymers. The anti-corrosion photoresist prepared by the invention has the characteristics of strong water solubility, high resolution, good heat resistance, high film stripping speed, good acid resistance and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sources of the substances to which the present invention relates are not limited in any particular way, and include, illustratively: phenolic epoxy resin: commercially available from Dakai ink chemical Co., ltd., model: n-738; the particle size of the calcium carbonate, the talcum powder, the transparent powder is 1500-3000 meshes; bentonite is available from Zhejiang Feng Hong, model: SMP-LP; polyfunctional acrylate monomer: trimethylolpropane acrylate TMGDA, available from taiwan chang, model: EM2104.
Example 1: a preparation method of an aqueous LED-UV etching-resistant electroplating photosensitive adhesive comprises the following steps:
step one: preparation of a water-soluble photosensitive resin:
S1: uniformly mixing 31g of phenolic epoxy resin, 30g of polyfunctional acrylate monomer and 3g of dimethylolbutyric acid, heating to 80 ℃, then slowly dropwise adding 70g of acrylic acid, 0.3g of catalyst triphenylphosphine and 0.1g of polymerization inhibitor p-hydroxyanisole, heating to 107 ℃ and reacting for 7 hours to obtain phenolic epoxy acrylate resin;
S2: adding 0.2g of polymerization inhibitor and 0.1g of catalyst into the prepared phenolic epoxy acrylate again, fully and uniformly stirring, adding 100g of maleic anhydride, heating to 110 ℃, reacting for 8 hours, and controlling the acid value to 68;
S3: adding 0.1g of polymerization inhibitor, cooling, slowly adding 9g of triethylamine under moderate speed stirring when the temperature is reduced to 45 ℃, and neutralizing until the pH value is 10; slowly dripping a mixture of diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water with the mass ratio of 75g to 10:80 under intense stirring to obtain water-soluble photosensitive resin;
Step two: the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps:
and uniformly mixing water-soluble photosensitive resin, water-based acrylic acid photosensitive monomer, water-based epoxy resin, photosensitive agent, photoinitiator, pigment, filler, wetting agent, dispersing agent, defoaming agent, water, thixotropic agent, leveling agent, multifunctional agent and film forming additive, and grinding to the fineness of 1-5 um to obtain the anti-etching electroplating photosensitive adhesive.
Example 2: a preparation method of an aqueous LED-UV etching-resistant electroplating photosensitive adhesive comprises the following steps:
step one: preparation of a water-soluble photosensitive resin:
S1: uniformly mixing 31g of phenolic epoxy resin, 30g of polyfunctional acrylate monomer and 3g of dimethylolbutyric acid, heating to 75 ℃, then slowly dropwise adding 70g of acrylic acid, 0.3g of catalyst triphenylphosphine and 0.1g of polymerization inhibitor p-hydroxyanisole, heating to 105 ℃ and reacting for 8 hours to obtain phenolic epoxy acrylate resin;
S2: adding 0.2g of polymerization inhibitor and 0.1g of catalyst into the prepared phenolic epoxy acrylate again, fully and uniformly stirring, adding 100g of maleic anhydride, heating to 105 ℃, reacting for 8 hours, and controlling the acid value to 68;
S3: adding 0.1g of polymerization inhibitor, cooling, slowly adding triethylamine or organic amine under moderate-speed stirring when the temperature is reduced to 50 ℃, and neutralizing until the pH value is 8-10; slowly dripping a mixture of diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water with the mass ratio of 75g to 10:80 under intense stirring to obtain water-soluble photosensitive resin;
Step two: the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps:
and uniformly mixing water-soluble photosensitive resin, water-based acrylic acid photosensitive monomer, water-based epoxy resin, photosensitive agent, photoinitiator, pigment, filler, wetting agent, dispersing agent, defoaming agent, water, thixotropic agent, leveling agent, multifunctional agent and film forming additive, and grinding to the fineness of 1-5 um to obtain the anti-etching electroplating photosensitive adhesive.
Example 3: a preparation method of an aqueous LED-UV etching-resistant electroplating photosensitive adhesive comprises the following steps:
step one: preparation of a water-soluble photosensitive resin:
s1: uniformly mixing 31g of phenolic epoxy resin, 30g of polyfunctional acrylate monomer and 3g of dimethylolbutyric acid, heating to 90 ℃, then slowly dropwise adding 70g of acrylic acid, 0.3g of catalyst triphenylphosphine and 0.1g of polymerization inhibitor p-hydroxyanisole, heating to 110 ℃ and reacting for 6 hours to obtain phenolic epoxy acrylate resin;
S2: adding 0.2g of polymerization inhibitor and 0.1g of catalyst into the prepared phenolic epoxy acrylate again, fully and uniformly stirring, adding 100g of maleic anhydride, heating to 115 ℃, reacting for 8 hours, and controlling the acid value to 68;
S3: adding 0.1g of polymerization inhibitor, cooling, slowly adding triethylamine or organic amine under moderate-speed stirring when the temperature is reduced to 50 ℃, and neutralizing until the pH value is 8-10; slowly dripping a mixture of diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water with the mass ratio of 75g to 10:80 under intense stirring to obtain water-soluble photosensitive resin;
Step two: the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps:
and uniformly mixing water-soluble photosensitive resin, water-based acrylic acid photosensitive monomer, water-based epoxy resin, photosensitive agent, photoinitiator, pigment, filler, wetting agent, dispersing agent, defoaming agent, water, thixotropic agent, leveling agent, multifunctional agent and film forming additive, and grinding to the fineness of 1-5 um to obtain the anti-etching electroplating photosensitive adhesive.
The components and parts by mass of the resist-plating photo-resist in examples 1 to 3 are shown in the following table 1:
TABLE 1
Comparative example 1: the procedure of example 1 was repeated except that the aqueous acrylic acid photosensitive monomer and the aqueous epoxy resin were not added.
Step one: preparation of a water-soluble photosensitive resin:
S1: uniformly mixing 31g of phenolic epoxy resin, 30g of polyfunctional acrylate monomer and 3g of dimethylolbutyric acid, heating to 80 ℃, then slowly dropwise adding 70g of acrylic acid, 0.3g of catalyst triphenylphosphine and 0.1g of polymerization inhibitor p-hydroxyanisole, heating to 107 ℃ and reacting for 7 hours to obtain phenolic epoxy acrylate resin;
S2: adding 0.2g of polymerization inhibitor and 0.1g of catalyst into the prepared phenolic epoxy acrylate again, fully and uniformly stirring, adding 100g of maleic anhydride, heating to 110 ℃, reacting for 8 hours, and controlling the acid value to 68;
S3: adding 0.1g of polymerization inhibitor, cooling, slowly adding 9g of triethylamine under moderate speed stirring when the temperature is reduced to 45 ℃, and neutralizing until the pH value is 10; slowly dripping a mixture of diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water with the mass ratio of 75g to 10:80 under intense stirring to obtain water-soluble photosensitive resin;
Step two: the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps:
The method comprises the steps of uniformly mixing water-soluble photosensitive resin, a photosensitizer, a photoinitiator, pigment, filler, a wetting agent, a dispersing agent, a defoaming agent, water, a thixotropic agent, a leveling agent, a multifunctional agent and a film forming auxiliary agent, and grinding the mixture to the fineness of 1-5 mu m to obtain the anti-etching electroplating photosensitive adhesive.
Comparative example 2: the water-soluble photosensitive resin prepared in comparative example 1 and the water-soluble photosensitive resin prepared in example 1 were mixed at a mass ratio of 1:1, and the total mass fraction was unchanged, to prepare an etching-resistant plating resist photosensitive paste, and the rest was the same as in example 1.
Uniformly mixing the water-soluble photosensitive resin prepared in comparative example 1, the water-soluble photosensitive resin prepared in example 1, a photosensitizer, a photoinitiator, pigment, filler, a wetting agent, a dispersing agent, a defoaming agent, water, a thixotropic agent, a leveling agent, a multifunctional agent and a film forming auxiliary agent, and grinding to the fineness of 1-5 mu m to obtain the anti-etching electroplating photosensitive adhesive;
wherein the mass ratio of the water-soluble photosensitive resin prepared in comparative example 1 to the water-soluble photosensitive resin prepared in example 1 is 1:1.
Experiment:
The resist pattern plating photo-resist adhesive prepared in examples 3 and comparative examples 1 to 2 was coated on the surface of a printed wiring board, and cured by exposure to an LED-UV light source to form a resist pattern coating having a thickness of 10 μm, which was subjected to performance test. The resist etching plating photoresist films prepared in examples 3 and comparative examples 1 to 2 were dried, exposed to light, and developed for 60 seconds using a tetramethylammonium hydroxide developer, and the adhesion properties of the samples were tested. The resist pattern was tested for release using a Hitachi S-4800 scanning electron microscope to characterize its adhesion properties. And (3) adopting a thermal analyzer, wherein the heating rate is 15 ℃/min, the temperature scanning range is 50-600 ℃, and the corresponding temperature is measured when the weight loss of the sample is 10%, so as to characterize the heat resistance. And etching the photoresist by adopting oxygen reaction ions, wherein the oxygen flow is 200sccm, the etching time is 5min, and the etching rate is calculated, so that the corrosion resistance of the photoresist is realized. Etch rate= (pre-etch film thickness-post-etch film thickness)/etch time.
Conclusion: as is clear from the comparison of the data on the table, in comparative example 1, the adhesion performance, heat resistance and etching resistance of the resist plating photo resist were all lowered without adding the aqueous acrylic photo-sensitive monomer or the aqueous epoxy resin. Comparative example 2 the water-soluble photosensitive resin prepared in comparative example 1 and the water-soluble photosensitive resin prepared in example 1 were mixed in a mass ratio of 1:1, and the total parts by mass was unchanged, and the adhesion property, heat resistance and etching resistance of the resist plating photoresist were inferior to those of the resist plating photoresist prepared in examples 1 to 3 of the present invention. Epoxy resin is added into the anti-etching electroplating photosensitive adhesive prepared in the embodiment 1 to the embodiment 3. The hydroxyl on the molecular chain of the epoxy resin is a strong polar group, the epoxy resin has strong adhesiveness to a metal substrate, and the C-C bond and ether bond in the polymer chain of the epoxy resin enable the epoxy resin to have good heat resistance and chemical resistance, so that the anti-etching electroplating photosensitive adhesive prepared by the invention has good adhesive property and the photoresist pattern does not fall off; and the heat resistance is also excellent, the corresponding temperature of the sample at 10% of the weight loss is 275-282 ℃, and compared with 224 ℃ in comparative example 1, the sample weight loss is obviously improved. And secondly, the epoxy group and the hydroxyl in the aqueous epoxy resin can be used as reaction points to be connected into the acrylic ester monomer, so that the aqueous epoxy resin has photo-curing activity. In addition to obtaining hydrophilic groups, the introduction of carboxyl groups further increases the molecular weight of the resin, so that the heat resistance and chemical solvent resistance are further improved. The epoxy group on the epoxy resin and carboxyl in acrylic ester undergo ring-opening reaction to introduce a photosensitive group C=C double bond, and the anti-etching electroplating photosensitive adhesive prepared by the invention has good adhesion performance, heat resistance and anti-etching performance.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. 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 (9)
1. A water-based LED-UV etching-resistant electroplating photosensitive adhesive is characterized in that: the light-sensitive adhesive consists of the following raw materials in parts by weight:
30-35 parts of water-soluble photosensitive resin, 8-20 parts of water-based acrylic photosensitive monomer, 8-10 parts of water-based epoxy resin, 0.5-2 parts of photosensitizer, 3-6 parts of photoinitiator, 0.3-2 parts of pigment, 5-16 parts of filler, 1 part of dispersing agent, 0.25-0.5 part of defoaming agent, 8-10 parts of water, 0.6-1.2 parts of thixotropic agent, 0.2-0.5 part of wetting agent, 0.5 part of leveling agent, 1 part of multifunctional agent and 5 parts of film forming auxiliary agent;
The water-soluble photosensitive resin comprises the following raw materials in parts by weight:
31 parts of phenolic epoxy resin, 25-40 parts of polyfunctional acrylate monomer, 3-5 parts of dimethylol butyric acid, 65-90 parts of acrylic acid, 0.3-0.7 part of catalyst triphenylphosphine, 0.2-0.75 part of polymerization inhibitor p-methoxyphenol or p-hydroxyanisole, 9-18 parts of organic base or organic amine, 98-147 parts of maleic anhydride or 192-230 parts of metabenzoic anhydride, 7-8 parts of diethylene glycol monomethyl ether, 7-8 parts of diethylene glycol diethyl ether acetate and 56-64 parts of distilled water.
2. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the aqueous acrylic photosensitive monomer is any one or more of difunctional acrylic ester, trifunctional acrylic ester and hexafunctional acrylic ester.
3. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the photosensitizer is one or more of benzophenone, 1173 and organophosphorus photosensitizers.
4. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the photoinitiator is any one or more of thioxanthone initiator, diaryl phosphine oxide compound initiator, UV-318 initiator, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethyl formyl-diphenyl phosphorus oxide.
5. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the pigment is one or more of phthalocyanine blue, ferric oxide blue and ferric green.
6. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the filler is any one or more of calcium carbonate, talcum powder, silicon dioxide and transparent powder.
7. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the defoamer is polysiloxane; the wetting agent is a biscytidine siloxane surfactant; the dispersing agent is any one or more of amino acrylic ester copolymer, phosphate and polybasic acid homopolymer; the thixotropic agent is bentonite.
8. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the preparation method of the water-soluble photosensitive resin comprises the following steps:
S1: uniformly mixing water-based novolac epoxy resin, acrylate monomer and dimethylolbutyric acid, heating to 75-90 ℃, then slowly dropwise adding acrylic acid, triphenylphosphine serving as a catalyst and p-hydroxyanisole serving as a polymerization inhibitor, heating to 105-110 ℃ and reacting for 6-8 hours to obtain novolac epoxy acrylate resin;
S2: adding the phenolic epoxy acrylate into the polymerization inhibitor para-hydroxyanisole and 0.1-0.2 part of catalyst triphenylphosphine again, fully and uniformly stirring, adding anhydride or phthalic anhydride, heating to 105-115 ℃, reacting for 8 hours, and controlling the acid value between 68-72;
s3: adding polymerization inhibitor, cooling, adding organic base or organic amine while stirring when the temperature is reduced to 40-50 ℃, and neutralizing until the pH value is 8-10; and dropwise adding a diethylene glycol monomethyl ether, diethylene glycol diethyl ether acetate and distilled water mixed solvent under stirring to obtain the water-soluble photosensitive resin.
9. The aqueous LED-UV etch resistant electroplated photosensitive paste of claim 1, wherein: the preparation method of the anti-etching electroplating photosensitive adhesive comprises the following steps: and uniformly mixing water-soluble photosensitive resin, water-based acrylic acid photosensitive monomer, water-based epoxy resin, acrylic ester, photosensitizer, photoinitiator, pigment, filler, wetting agent, dispersing agent, defoaming agent, water and thixotropic agent, and grinding to the fineness of 1-5 um to obtain the anti-etching electroplating photosensitive adhesive.
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| CN202410308810.7A CN118068647A (en) | 2024-03-19 | 2024-03-19 | Water-based LED-UV (light-emitting diode-ultraviolet) anti-etching electroplating photosensitive adhesive |
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