CN117264465B - Non-cracking exposure development type solder resist plug hole ink and preparation method thereof - Google Patents
Non-cracking exposure development type solder resist plug hole ink and preparation method thereof Download PDFInfo
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- CN117264465B CN117264465B CN202311248428.3A CN202311248428A CN117264465B CN 117264465 B CN117264465 B CN 117264465B CN 202311248428 A CN202311248428 A CN 202311248428A CN 117264465 B CN117264465 B CN 117264465B
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- epoxy resin
- exposure
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- 238000005336 cracking Methods 0.000 title claims abstract description 58
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000011161 development Methods 0.000 title claims description 27
- 239000002904 solvent Substances 0.000 claims abstract description 63
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003822 epoxy resin Substances 0.000 claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 56
- 239000000945 filler Substances 0.000 claims abstract description 53
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 27
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 101
- 238000002156 mixing Methods 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 62
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 58
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical group N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 56
- 229910052582 BN Inorganic materials 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000004843 novolac epoxy resin Substances 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
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- 239000012745 toughening agent Substances 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
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- 230000003078 antioxidant effect Effects 0.000 claims description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 claims description 2
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
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- 239000011259 mixed solution Substances 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 150000002924 oxiranes Chemical class 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 4
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 41
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 26
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- 230000000052 comparative effect Effects 0.000 description 20
- 235000011187 glycerol Nutrition 0.000 description 18
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 13
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
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- 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 description 3
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- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a non-cracking exposure developing type solder mask plug hole ink and a preparation method thereof, wherein the non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B, and the component A comprises the following components in parts by mass: 10-50 parts of alkali-soluble o-cresol formaldehyde epoxy resin, 1-10 parts of active monomer, 1-10 parts of CTBN (methyl methacrylate-butadiene-styrene), 30-150 parts of modified filler, 1-10 parts of photoinitiator and 1-20 parts of solvent; the component B comprises the following components in parts by weight: 1-10 parts of epoxy resin, 1-10 parts of auxiliary agent and 1-10 parts of solvent; wherein the modified filler is obtained by reacting glycerol, sodium methoxide, glycidol and inorganic filler. The modified filler has good dispersibility and compatibility, can obviously improve the mechanical properties of the hole plugging ink after being compounded with toughening components such as CTBN, has the characteristics of no cracking and high strength, and overcomes the defects in the prior art.
Description
Technical Field
The invention relates to the technical field of solder resist ink, in particular to a non-cracking exposure development type solder resist plug hole ink and a preparation method thereof.
Background
With the development of electronic products in the direction of light, thin, short and small, a double-layer board or a multi-layer circuit board (PCB) is also developed in the direction of high density and high difficulty, and a large number of SMT and BGA PCBs are generated. The via hole in the PCB plays a role of connecting and conducting the circuit, and the customer requires the hole plugging when mounting the component, the hole plugging has 5 roles: (1) The plug hole can prevent tin from penetrating through the element surface from the via hole to cause short circuit when the PCB passes wave soldering; especially, when the via hole is placed on the BGA bonding pad, the via hole must be plugged first, and then gold plating treatment is carried out, so that the BGA bonding is facilitated; (2) avoiding soldering flux to remain in the via hole; (3) The PCB is guaranteed to be vacuumized on a testing machine to form negative pressure after surface mounting and component assembling are completed; (4) Preventing the surface solder paste from flowing into the holes to cause cold joint and affecting the mounting; and (5) preventing tin balls from popping up to cause short circuit when wave soldering is performed.
The traditional hole plugging technology adopts resin hole plugging, and can solve the problem that common ink is not easy to be plugged by selecting solvent-free thermosetting resin containing a large amount of filler, and simultaneously, cracks are not easy to generate in the hole plugging, so that the method can be used for high-aspect ratio aperture filling. However, baking, grinding and leveling are needed after the resin is plugged, and then the solder resist ink is coated, so that compared with the exposure development type plugging ink, the resin is plugged by more leveling and high-temperature baking processes, and the process is more complex. The common exposure development type hole plugging ink has the problems that the volume is obviously shrunk in the curing process and the hole plugging is insufficient because the ink system contains a solvent and double bonds; meanwhile, the adhesion force of the ink to copper in the through hole is good, cracks can be generated in the ink when the ink is solidified and contracted, the material absorbs moisture due to the existence of the cracks, the board is easier to burst, and the requirement on the product performance cannot be met. Therefore, how to provide a solder mask plug hole ink with difficult cracking, high mechanical property and high stability is a problem to be solved in the field.
In view of the foregoing, it is necessary to develop a new technical solution to solve the drawbacks of the prior art.
Disclosure of Invention
Based on the above, the invention provides a non-cracking exposure developing type solder mask plug hole ink and a preparation method thereof. The modified filler is prepared by reacting glycerol, sodium methoxide, glycidol and inorganic filler, introduces an alkoxy chain segment with a branched structure and a large number of hydroxyl groups on the surface of the inorganic filler, has good dispersibility and compatibility, can obviously improve the mechanical properties of the hole plugging ink after being compounded with alkali-soluble o-cresol formaldehyde epoxy resin, CTBN (carboxyl terminated nitrile rubber), auxiliary agent and other components, has the characteristics of no cracking, high strength, high stability and the like, and overcomes the defects in the prior art.
An object of the present invention is to provide a non-cracking exposure-developing type solder resist plug ink composed of a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
1-10 parts of epoxy resin
1-10 Parts of auxiliary agent
1-10 Parts of a solvent;
wherein,
The modified filler is obtained by reacting glycerol, sodium methoxide, glycidol and inorganic filler.
Further, the inorganic filler is selected from one or more of silicon dioxide, carbonate, sulfate, talcum powder, mica powder, silicon micropowder, kaolin, wollastonite, metal oxide, metal hydroxide, carbon nano tube, boron nitride and graphene.
Further, the reactive monomer is a monomer having a monofunctional or polyfunctional acrylate unit.
Specifically, selectable objects of the reactive monomer include, but are not limited to: monomers containing an acrylate unit such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, cetyl acrylate, stearyl acrylate, etc., or methyl methacrylate, ethyl methacrylate, propyl ethacrylate, butyl acrylate, octyl acrylate, dodecyl propyl acrylate, stearyl butyl acrylate, etc., in short, the ester group may be linked to a C1-C22 alkyl chain structure, and the alkyl chain moiety linked to acrylic acid may be a C1-C22 alkyl chain structure;
Monomers containing two acrylate units, such as diethylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, tetraethylene glycol diacrylate, and the like; the ester group of the acrylic ester can be independently connected with an alkyl chain structure of C1-C22;
monomers containing three acrylate units, such as trimethylolpropane triacrylate, 1,2, 3-propane triacrylate, tri (2-hydroxyethyl) isocyanuric acid triacrylate, etc., wherein the acrylate groups may independently be linked to a C1-C22 alkyl chain structure;
Monomers containing 4 to 6 acrylate units, such as polydipentaerythritol hexaacrylate, the ester groups of the acrylate may be independently linked to a C1-C22 alkyl chain structure;
And a mixture of any two or more of the above monomers having a monofunctional or polyfunctional acrylate unit blended at any mass ratio. The blending may be binary blending, ternary blending, quaternary blending or more.
Further, the auxiliary agent is selected from one or more of toner, flatting agent, defoamer, ultraviolet absorber, dispersant, antioxidant and flexibilizer.
The toner may be, but is not limited to: phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, naphthalene black, and the like.
Leveling agents may be, but are not limited to: silicone, polyurethane, alcohol, polyalcohol, acrylic, inorganic, etc., such as isopropyl alcohol, polysiloxane, dimethicone, glycerin, polyether, alumina, calcium oxide, etc., and mixtures of any of the above alternatives blended in any mass ratio.
The dispersant may be, but is not limited to: anionic surfactant series such as AES, AOS, LAS, MES and the like; a non-ionic surfactant series, such as the AEO series, the span series, the tween series, etc., and mixtures of any of the above alternatives blended in any mass ratio.
Defoamers may be, but are not limited to: mineral oil, polydimethyl silicone oil, tributyl phosphate, silicone resin, and the like, and mixtures of any of the above alternatives, blended in any mass ratio.
The ultraviolet absorber may be, but is not limited to: benzophenone, benzotriazole, acrylonitrile, triazine, and the like, and mixtures of any of the foregoing alternatives, blended in any mass ratio.
Antioxidants may be, but are not limited to: phenols, thiols, etc., and mixtures of any of the above alternatives, blended in any mass ratio.
Toughening agents may be, but are not limited to: rubber-based toughening agents, resin-based toughening agents, and the like, such as ethylene propylene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, styrene butadiene rubber, SBS, ABS, MBS, CPE, DOP, DBP, TCP, TPP, and the like, and mixtures of any of the above alternatives, blended in any mass ratio.
Further, the dispersant is selected from anionic surfactants, preferably one or more of dodecylbenzene sulfonate, dodecylsulfate, lunar silicate, stearate.
Further, the epoxy resin is selected from one or more of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butylphenol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate and bicyclo-diene epoxide.
Further, the solvent is selected from organic solvents such as methanol, ethanol, propanol, butanol, chlorobenzene, toluene, tetrahydrofuran, dichloromethane, chloroform, petroleum ether, benzene, DMF, DMSO, DBE, or derivatives of the above alternatives, and mixtures of any of the above alternatives blended in any mass ratio.
The invention also provides a preparation method of the non-cracking exposure and development type solder mask hole plugging ink, which comprises the following steps:
s1, adding inorganic filler into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated filler;
S2, mixing glycerol and sodium methoxide, stirring, heating, reacting, vacuumizing, adding a solvent, heating, stirring, adding glycidol, preserving heat, reacting, and purifying to obtain modified polyglycidyl ether;
s3, blending the carboxylated filler with an activator, adding modified polyglycidyl ether, performing ultrasonic reaction, and purifying to obtain modified filler;
S4, blending alkali-soluble o-cresol formaldehyde epoxy resin, an active monomer, CTBN, modified filler, a photoinitiator and a solvent to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding and filtering to obtain a product.
In step S1, the strong acid solution is a mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid with the volume ratio of (3-5) being 1, and the ultrasonic treatment time is 6-12h.
Further, in the step S2, the temperature of the stirring and heating reaction is 30-60 ℃ and the time is 1-3h; the temperature of heating and stirring is 90-100 ℃ and the time is 10-14h; the reaction time of the heat preservation is 4-6h.
Further, in the step S3, the mass ratio of the carboxylated filler to the modified polyglycidyl ether is 1 (4-10), and the ultrasonic reaction time is 20-40h.
Further, the activators are 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (edc.hcl) and 4-Dimethylaminopyridine (DMAP).
Further, step S1 includes the steps of: 1L of concentrated sulfuric acid (concentration: 98%) and 0.25L of concentrated hydrochloric acid (concentration: 37.5%) were mixed, then 15g of boron nitride was added, and the resultant was sonicated at 50℃for 8 hours (power: 500W), washed to neutrality with deionized water and ethanol, and then dried at 60℃overnight to obtain carboxylated boron nitride.
Further, step S2 includes the steps of: mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained.
Further, step S3 includes the steps of: and (3) taking N, N-dimethylformamide as a solvent, blending the carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding the modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain the modified filler.
Further, the preparation method of the alkali-soluble epoxy acrylic resin comprises the following steps:
adding o-cresol novolac epoxy resin and acrylic acid into diethylene glycol monoethyl ether acetate, stirring at 80-100 ℃, adding triphenylphosphine, heating to 100-110 ℃ for reaction for 1-2h, heating to 120-140 ℃ for reaction for 10-12h, adding dibasic ester and tetrahydrophthalic anhydride, reacting for 2-4h at 100-110 ℃, and cooling to obtain the alkali-soluble epoxy acrylic resin.
Another object of the present invention is to provide the use of the above-mentioned non-cracking exposure-developing solder resist plug ink in PCB substrates.
The invention has the following beneficial effects:
The non-cracking exposure developing type solder resist plug hole ink provided by the invention adopts modified filler as a component, the component firstly takes glycerol, sodium methoxide and glycidol as raw materials to prepare modified polyglycidyl ether with hyperbranched structure, and then the modified polyglycidyl ether is adopted to react with surface carboxylation inorganic filler, so that a large number of alkoxy chain segments, ether bonds and a large number of hydroxyl groups with branched structures are introduced on the surface of the filler, the dispersibility of the filler is enhanced, and the phenomena of aggregation and uneven dispersion of a large number of fillers can be avoided; the compatibility between the modified filler and the resin is greatly improved, the modified filler is beneficial to cross-linking with epoxy groups in the epoxy resin, carboxyl groups in CTBN and other active groups, and a synergistic effect is generated, so that a more three-dimensional net structure is formed, the toughness is enhanced, the internal stress in the ink preparation and application process can be released, the generation of bubbles and cracks is prevented, and the mechanical property of a product is improved; on the other hand, the oxygen-containing functional groups of the components can form hydrogen bonds, the stability of the ink product and the coating is further improved through intermolecular force, and the ink can be stored and used for a long time under various conditions. Therefore, the invention solves the defects in the prior art and has good application prospect.
Drawings
Fig. 1 shows the appearance of the jack ink of example 1 and comparative example 1 after baking at high temperature, wherein fig. 1 (a) is the appearance of example 1 and fig. 1 (b) is the appearance of comparative example 1.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
The words "preferred," "more preferred," and the like in the present disclosure refer to embodiments of the present disclosure that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that, except in any operating examples, or where otherwise indicated, quantities or all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The epoxy resin in the embodiment of the invention is bisphenol A epoxy resin E-12.
The active monomers in the embodiment of the invention are trimethylolpropane triacrylate (TMPTA) and polydipentaerythritol hexaacrylate (DPHA) with the mass ratio of 1:1.
The CTBN in the embodiment of the invention is carboxyl-terminated liquid nitrile rubber purchased from Lanzhou petrochemical industry, and has a carboxyl value: 0.464mmol/g.
The photoinitiator in the embodiment of the invention is ITX and 819.
The auxiliary agent in the embodiment of the invention comprises toner, a leveling agent and a dispersing agent in a mass ratio of 1:1:2, wherein the toner is phthalocyanine green, the leveling agent is isopropanol, and the dispersing agent is sodium dodecyl sulfate.
The solvent in the examples of the present invention is dibasic ester (DBE).
The boron nitride in the examples of the present invention was analytically pure and purchased from ala Ding Shiji inc.
In the embodiment of the invention, the preparation method of the alkali-soluble o-cresol formaldehyde epoxy resin comprises the following steps:
535 parts of o-cresol novolac epoxy resin (EPICLON N-695 from DIC corporation) and 180 parts of acrylic acid are added to 300 parts of diethylene glycol monoethyl ether acetate, and the mixture is heated to 100 ℃ and stirred, and dissolved until uniform; then adding 2 parts of triphenylphosphine, heating to 110 ℃ for reaction for 2 hours, heating to 120 ℃ and then carrying out reaction for 12 hours; 415 parts of dibasic ester and 250 parts of tetrahydrophthalic anhydride are added into the obtained reaction solution, the reaction is carried out for 4 hours at 110 ℃, and after cooling, the alkali-soluble o-cresol formaldehyde epoxy resin is obtained.
In the embodiment of the invention, "parts" refer to parts by weight.
Example 1
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
1 part of epoxy resin
Auxiliary 1 part
1 Part of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 2
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
Epoxy resin 5 parts
Auxiliary agent 5 parts
5 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 3
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
1 part of epoxy resin
Auxiliary 1 part
1 Part of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 4
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
2 parts of epoxy resin
Auxiliary 2 parts
2 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 5
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
2.5 parts of epoxy resin
2.5 Parts of auxiliary agent
2.5 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 6
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
2 parts of epoxy resin
Auxiliary 2 parts
2 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 7
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
3 parts of epoxy resin
Auxiliary agent 3 parts
3 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 8
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
4 parts of epoxy resin
Auxiliary agent 4 parts
4 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 9
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
3 parts of epoxy resin
Auxiliary agent 3 parts
3 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 10
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
4 parts of epoxy resin
Auxiliary agent 4 parts
4 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 11
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
10 parts of epoxy resin
Auxiliary agent 10 parts
10 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Example 12
A non-cracking exposure developing type solder mask plug hole ink comprises a component A and a component B,
The component A comprises the following components in parts by weight:
The component B comprises the following components in parts by weight:
6 parts of epoxy resin
Auxiliary agent 5 parts
5 Parts of solvent;
The preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
S1, mixing 1L of concentrated sulfuric acid (with the concentration of 98%) and 0.25L of concentrated hydrochloric acid (with the concentration of 37.5%), then adding 15g of boron nitride, performing ultrasonic treatment at 50 ℃ for 8 hours (with the power of 500W), washing the product to be neutral by deionized water and ethanol, and then drying at 60 ℃ overnight to obtain carboxylated boron nitride;
s2, mixing 0.1mol of glycerol and 0.01mol of sodium methoxide, stirring at 30 ℃ for reaction for 1.5 hours, then heating to 60 ℃, and vacuumizing until no bubbles are generated in a reaction system; then 20mL of 1, 4-dioxane is added, the temperature is raised to 95 ℃, 2.1mol of glycidol is added in 10 hours under stirring, then the heat preservation reaction is continued for 5 hours, and the 1, 4-dioxane is removed under reduced pressure, so that the modified polyglycidyl ether is obtained;
S3, taking N, N-dimethylformamide as a solvent, blending carboxylated boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding modified polyglycidyl ether (carboxylated boron nitride: modified polyglycidyl ether: EDC, HCl: DMAP=1:6:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain modified filler;
S4, blending the modified filler, the alkali-soluble o-cresol formaldehyde epoxy resin, the active monomer, CTBN, the photoinitiator and the solvent according to the parts by weight to obtain a component A; and (3) blending epoxy resin, an auxiliary agent and a solvent to obtain a component B, blending the component A and the component B, uniformly stirring and dispersing, grinding until the fineness is less than or equal to 20 mu m, and sieving with a 120-mesh sieve to obtain a product.
Comparative example 1
The difference between the exposure developing type solder resist plug hole ink and the comparative example 1 is that: in step S4, the modified filler was replaced with unmodified boron nitride in equal mass, and the other components and the production method were the same as in example 1.
Comparative example 2
The difference between the exposure developing type solder resist plug hole ink and the comparative example 1 is that: in step S3, the modified polyglycidyl ether and other components are replaced by polyethylene glycol (PEG-400) to obtain polyethylene glycol modified filler, and other components and preparation methods are the same as in example 1.
Comparative example 3
The difference between the exposure developing type solder resist plug hole ink and the comparative example 1 is that: in step S4, the same mass as CTBN was replaced with MBS toughening agent (Brillouin MZ-120), and the other components and preparation method were the same as in example 1.
Test case
Performance tests were performed on the exposure developing type solder resist plug hole inks prepared in examples 1 to 3 and comparative examples 1 to 3.
The test method is as follows:
The exposure and development type solder resist plug hole inks prepared in examples and comparative examples were applied to a substrate plated with a 30 μm copper layer and having an electric via hole of 1mm diameter, respectively, and then photo-cured for 1 hour (ultraviolet light of wavelength 395nm, intensity 25.0mW/cm 2) and thermally cured at 150℃for 1 hour.
Pencil hardness: measured based on JIS K5400.
Adhesion: the films were each scored x-shaped with a needle tip, then attached to the score with cellophane adhesive tape and pulled, as assessed according to the following criteria:
excellent: not torn off;
common: tearing off a small amount;
poor: a large amount of the paper is torn off.
Bending resistance: 180 ° bending was performed with the solder resist ink film as the outer side, and evaluation was performed with the following criteria:
Excellent: the film has no cracks;
poor: the film had cracks.
Acid/alkali resistance: at 20 ℃, the PCB circuit board coated with the solder resist ink is immersed in 10% sulfuric acid solution or 10% sodium hydroxide solution, taken out after 30min, and the state and the adhesiveness of the coating film are evaluated, and the judgment standard is as follows:
Qualified: no or slight changes were found;
Disqualification: the coating film is swelled or swelled and falls off.
Heat resistance: the thermal shock performance test was carried out according to the method of IPC-SM-840E 3.9.3, and the criterion was as follows:
qualified: no bubbles or cracks;
Disqualification: air bubbles and cracking occur.
And (3) reflow soldering test: and (5) reflow soldering is carried out, wherein the judgment standard is as follows:
Qualified: no cracking or swelling;
disqualification: cracking and swelling.
The test results are shown in Table 1.
TABLE 1 Performance test results
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hardness of pencil | 4H | 4H | 4H | 2H | 3H | 3H |
| Adhesion force | Excellent and excellent properties | Excellent and excellent properties | Excellent and excellent properties | Poor quality | Ordinary use | Ordinary use |
| Bending resistance | Excellent and excellent properties | Excellent and excellent properties | Excellent and excellent properties | Poor quality | Poor quality | Excellent and excellent properties |
| Acid resistance | Qualified product | Qualified product | Qualified product | Failure to pass | Qualified product | Qualified product |
| Alkali resistance | Qualified product | Qualified product | Qualified product | Failure to pass | Qualified product | Qualified product |
| Heat resistance | Qualified product | Qualified product | Qualified product | Failure to pass | Failure to pass | Failure to pass |
| Reflow test | Qualified product | Qualified product | Qualified product | Failure to pass | Failure to pass | Failure to pass |
| Cracking in holes | Without any means for | Without any means for | Without any means for | Cracking of | Cracking of | Cracking of |
Fig. 1 shows the appearance of the jack ink of example 1 and comparative example 1 after baking at high temperature, wherein fig. 1 (a) is the appearance of example 1 and fig. 1 (b) is the appearance of comparative example 1.
As can be seen from fig. 1, the plug hole prepared in example 1 has no cracking phenomenon and good morphology, while comparative example 1 has a large amount of cracking.
As can be seen from table 1, the performances of the non-cracking exposure developing type solder resist plug hole ink prepared in the embodiment of the invention are obviously superior to those of comparative examples 1-3, the modified filler is replaced by unmodified boron nitride in comparative example 1, and the modified polyglycidyl ether is replaced in comparative example 2, so that the dispersibility and compatibility of the filler are reduced, a three-dimensional net structure is difficult to form, and the stability and mechanical properties of the product are reduced; whereas comparative example 3 replaces CTBN, resulting in reduced synergy between the components and less than ideal performance improvement. The non-cracking exposure developing type solder resist plug hole ink disclosed by the invention keeps stronger heat resistance, greatly improves the mechanical strength, overcomes the defects in the prior art, and has a good application prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. A non-cracking exposure developing type solder resist plug hole ink is characterized in that the non-cracking exposure developing type solder resist plug hole ink consists of a component A and a component B,
The component A comprises the following components in parts by weight:
10-50 parts of alkali-soluble o-cresol formaldehyde epoxy resin
1-10 Parts of active monomer
CTBN 1-10 parts
30-150 Parts of modified filler
1-10 Parts of photoinitiator
1-20 Parts of a solvent;
The component B comprises the following components in parts by weight:
1-10 parts of epoxy resin
1-10 Parts of auxiliary agent
1-10 Parts of a solvent;
wherein,
The modified filler is obtained by reacting glycerol, sodium methoxide, glycidol and inorganic filler;
The inorganic filler is boron nitride;
the preparation method of the non-cracking exposure development type solder mask plug hole ink comprises the following steps:
s1, adding inorganic filler into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated filler;
S2, mixing glycerol and sodium methoxide, stirring, heating, reacting, vacuumizing, adding a solvent, heating, stirring, adding glycidol, preserving heat, reacting, and purifying to obtain modified polyglycidyl ether;
s3, blending the carboxylated filler with an activator, adding modified polyglycidyl ether, performing ultrasonic reaction, and purifying to obtain modified filler;
S4, blending alkali-soluble o-cresol formaldehyde epoxy resin, an active monomer, CTBN, modified filler, a photoinitiator and a solvent to obtain a component A; mixing epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, uniformly stirring and dispersing, grinding and filtering to obtain a product;
The activator is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine.
2. The non-cracking exposure and development type solder resist plug ink according to claim 1, wherein the auxiliary agent is one or more selected from the group consisting of toner, leveling agent, defoamer, ultraviolet absorber, dispersant, antioxidant and toughening agent.
3. The non-cracking exposure-developing solder resist plug ink according to claim 1, wherein the reactive monomer is a monomer having a monofunctional or polyfunctional acrylate unit.
4. The non-cracking exposure and development type solder resist plug ink according to claim 1, wherein the epoxy resin is selected from one or more of bisphenol a type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butylphenol novolac epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate, and dicyclodiene epoxide.
5. The non-cracking exposure and development type solder resist plug hole ink according to claim 1, wherein in the step S1, the strong acid solution is a mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid with the volume ratio of (3-5): 1, and the ultrasonic treatment time is 6-12 h.
6. The non-cracking exposure and development type solder mask plug hole ink according to claim 1, wherein in the step S2, the temperature of the stirring and heating reaction is 30-60 ℃ and the time is 1-3 h; the temperature of the heating and stirring is 90-100 ℃ and the time is 10-14 h; the time of the heat preservation reaction is 4-6 h.
7. The non-cracking exposure and development type solder resist plug hole ink according to claim 1, wherein in the step S3, the mass ratio of the carboxylated filler to the modified polyglycidyl ether is 1 (4-10), and the time of the ultrasonic reaction is 20-40 h.
8. Use of the non-cracking exposure and development type solder mask hole ink as claimed in any one of claims 1 to 7 in a PCB substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311248428.3A CN117264465B (en) | 2023-09-26 | 2023-09-26 | Non-cracking exposure development type solder resist plug hole ink and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311248428.3A CN117264465B (en) | 2023-09-26 | 2023-09-26 | Non-cracking exposure development type solder resist plug hole ink and preparation method thereof |
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| Publication Number | Publication Date |
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| CN117264465A CN117264465A (en) | 2023-12-22 |
| CN117264465B true CN117264465B (en) | 2024-04-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911402A (en) * | 2012-10-16 | 2013-02-06 | 广东工业大学 | Preparation method of star-shaped heat conducting filler with multiple heat conducting points |
| CN113698668A (en) * | 2021-10-27 | 2021-11-26 | 潍坊学院 | Method for stabilizing metal/graphene dispersion system through polyglycidyl ether functionalization |
| CN115584161A (en) * | 2022-09-21 | 2023-01-10 | 佛山市西伦化工有限公司 | Hole plugging ink composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911402A (en) * | 2012-10-16 | 2013-02-06 | 广东工业大学 | Preparation method of star-shaped heat conducting filler with multiple heat conducting points |
| CN113698668A (en) * | 2021-10-27 | 2021-11-26 | 潍坊学院 | Method for stabilizing metal/graphene dispersion system through polyglycidyl ether functionalization |
| CN115584161A (en) * | 2022-09-21 | 2023-01-10 | 佛山市西伦化工有限公司 | Hole plugging ink composition and preparation method and application thereof |
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