CN117126565B - Anti-welding ink based on DCPD phenolic epoxy resin and preparation method thereof - Google Patents
Anti-welding ink based on DCPD phenolic epoxy resin and preparation method thereof Download PDFInfo
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- CN117126565B CN117126565B CN202311117996.XA CN202311117996A CN117126565B CN 117126565 B CN117126565 B CN 117126565B CN 202311117996 A CN202311117996 A CN 202311117996A CN 117126565 B CN117126565 B CN 117126565B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003466 welding Methods 0.000 title description 5
- 229910000679 solder Inorganic materials 0.000 claims abstract description 31
- 229910052582 BN Inorganic materials 0.000 claims abstract description 27
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 16
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 15
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 15
- -1 polyoxypropylene Polymers 0.000 claims abstract description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000004843 novolac epoxy resin Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229920003986 novolac Polymers 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a DCPD phenolic epoxy resin-based solder resist ink and a preparation method thereof, wherein the solder resist ink comprises a component A and a component B, and the component A comprises the following components in parts by weight: 30-60 parts of epoxy acrylic resin, 6-12 parts of UV monomer, 3-8 parts of modified filler, 1-3 parts of photoinitiator, 1-6 parts of auxiliary agent and 10-50 parts of solvent; the component B comprises the following components in parts by weight: 1-10 parts of DCPD phenolic epoxy resin, 1-10 parts of bisphenol A epoxy resin and a solvent; the modified filler is trihydroxy polyoxypropylene ether modified hexagonal boron nitride. The invention adopts the DCPD phenolic epoxy resin, the acrylic resin and the bisphenol A epoxy resin to compound, and adopts the modified hexagonal boron nitride as the filler, thereby generating good synergistic effect, effectively improving the compatibility and the crosslinking density among various components, and leading the ink coating to have lower dielectric constant and better stability and mechanical property.
Description
Technical Field
The invention relates to the technical field of solder resist ink, in particular to a DCPD phenolic epoxy resin-based solder resist ink and a preparation method thereof.
Background
With the continuous progress of network and communication technologies, components such as copper-clad plates, circuit boards and the like used in electronic products are required to have higher reliability and higher speed, and related manufacturers have raised higher and higher requirements in the aspects of dielectric constant, dielectric loss factor, heat resistance and the like. And how to reduce the dielectric constant and dielectric loss of the solder resist ink serving as an important component of the PCB becomes the focus of research in the field.
The existing solder resist ink product usually uses phenolic epoxy resin as a matrix, is compounded with components such as epoxy resin, UV monomer and the like to form a solder resist ink composition, and is heated and hardened after ultraviolet hardening to obtain a coating film, however, the product has the defects that the product is difficult to meet the transmission requirement of electronic signals and has larger defects. Increasing the content of functional fillers with low dielectric constants overcomes the drawbacks of dielectric properties, but may affect the compatibility between the components, resulting in reduced product stability, mechanical properties. Therefore, how to provide a solder resist ink with low dielectric constant, high mechanical property, heat conduction and other performances 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 solder resist ink based on DCPD phenolic epoxy resin and a preparation method thereof. The invention adopts DCPD phenolic epoxy resin, acrylic resin and bisphenol A epoxy resin to compound, and adopts trihydroxy polyoxypropylene ether modified hexagonal boron nitride as filler, thereby generating good synergistic effect, effectively improving compatibility and crosslinking density among various components, and leading the ink coating to have lower dielectric constant and better stability and mechanical property.
It is an object of the present invention to provide a DCPD novolac epoxy based solder resist ink comprising an a component and a B component,
the component A comprises the following components in parts by weight:
a solvent;
the component B comprises the following components in parts by weight:
1-10 parts of DCPD phenolic epoxy resin
Bisphenol A epoxy resin 1-10 parts
A solvent;
wherein,
the modified filler is trihydroxy polyoxypropylene ether modified hexagonal boron nitride.
Further, the preparation method of the modified filler comprises the following steps:
s1, adding hexagonal boron nitride into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated hexagonal boron nitride;
s2, blending the carboxylated hexagonal boron nitride with an activating agent, adding trihydroxy polyoxypropylene ether, carrying out ultrasonic reaction, and purifying to obtain the modified filler.
Further, the strong acid solution is a mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid with the volume ratio of (3-5): 1.
Further, in step S1, the time of the ultrasonic treatment is 6-12 hours.
Further, in step S2, the time of the ultrasonic reaction is 20-40 hours.
Further, in the step S2, the mass ratio of the carboxylated hexagonal boron nitride to the trihydroxy polyoxypropylene ether is 1 (4-10).
Further, the activator is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl) and 4-Dimethylaminopyridine (DMAP) in a mass ratio of (2-6) 1.
Further, the mass ratio of the carboxylated hexagonal boron nitride to the trihydroxy polyoxypropylene ether to the EDC, HCl to the DMAP is 1 (4-10): 2-6): 1.
Further, the epoxy equivalent of the DCPD phenolic epoxy resin is 250-300g/eq.
The invention also provides a preparation method of the DCPD phenolic epoxy resin-based solder resist ink, which comprises the following steps:
blending alkali-soluble epoxy acrylic resin, UV monomer, modified filler, photoinitiator, auxiliary agent and solvent to obtain a component A; and (3) blending DCPD phenolic epoxy resin, bisphenol A epoxy resin 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.
Further, the UV monomer is selected from monomers containing acrylic acid units, the auxiliary agent is selected from one or more of leveling agents, defoamers, ultraviolet absorbers, dispersants and antioxidants, and the solvent is selected from toluene or derivative solvents thereof.
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.
The invention further aims to provide application of the DCPD phenolic epoxy resin-based solder resist ink in a PCB.
The invention has the following beneficial effects:
the solder resist ink provided by the invention adopts the specific DCPD phenolic epoxy resin as matrix resin to be compounded with the alkali-soluble epoxy acrylic resin and bisphenol A resin, and has the characteristics of good thermal stability and lower dielectric constant; in addition, the hexagonal boron nitride filler is modified, firstly, carboxylation treatment is carried out on the hexagonal boron nitride, and the introduction of carboxyl can destroy a conjugated structure, improve the insulativity of the hexagonal boron nitride, simultaneously facilitate the subsequent reaction and improve the grafting rate; after the modified filler reacts with the trihydroxy polyoxypropylene ether, the surface of the hexagonal boron nitride is introduced with an alkoxy chain segment with a branched structure and also has a large number of hydroxyl groups and ether bonds, so that on one hand, the compatibility between the modified filler and the resin is greatly improved, and the modified filler is easy to crosslink with active groups such as epoxy groups in DCPD phenolic epoxy resin and alkali-soluble epoxy acrylic resin to form a more three-dimensional network structure, thereby improving the mechanical property of the product; on the other hand, a plurality of oxygen-containing functional groups can form hydrogen bonds, so that the stability of the ink is further improved, the ink can be stored and used under a plurality of conditions, and the ink has good application prospect.
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 bisphenol A epoxy resin in the embodiment of the invention is bisphenol A epoxy resin E-12.
The DCPD phenolic epoxy resin in the embodiment of the invention is named as Taiwan vinca DNE260, and the epoxy equivalent is 255-285g/eq.
The UV monomers in the embodiment of the invention are trimethylolpropane triacrylate (TMPTA) and polydipentaerythritol hexaacrylate (DPHA) with the mass ratio of 1:1.
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 2:1:1, wherein the toner is carbon black, 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).
In the embodiment of the invention, "parts" refer to parts by weight.
The preparation method of the modified hexagonal boron nitride in the embodiment of the invention 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 hexagonal boron nitride, carrying out 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 hexagonal boron nitride;
s2, taking N, N-dimethylformamide as a solvent, blending carboxylated hexagonal boron nitride with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding trihydroxy polyoxypropylene ether (carboxylated hexagonal boron nitride: trihydroxy polyoxypropylene ether: EDC, HCl: DMAP=1:8:4:1, m/m/m), performing ultrasonic reaction for 24h, washing with water and ethanol, centrifuging, and freeze-drying to obtain the modified filler.
The synthesis process of the alkali-soluble epoxy acrylic resin in the embodiment of the invention comprises the following steps:
to 300g of diethylene glycol monoethyl ether acetate, 535g of o-cresol novolac epoxy resin (EPICLON N-695 manufactured by DIC Co., ltd.) and 180g of acrylic acid were added, and the mixture was heated to 100℃and stirred, and dissolved until uniform. Then 2g of triphenylphosphine is added, the mixture is heated to 110 ℃ for reaction for 2 hours, and then the mixture is heated to 120 ℃ for reaction for 12 hours. 415g of dibasic ester and 250.0g of tetrahydrophthalic anhydride were added to the obtained reaction solution, and the reaction was carried out at 110℃for 4 hours, followed by cooling to obtain an alkali-soluble epoxy acrylic resin having an acid value of 89mgKOH/g as a solid component and 65% as a solid component.
Example 1
A solder resist ink based on DCPD phenolic epoxy resin comprises an A component and a B component,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
5 parts of DCPD phenolic epoxy resin
Bisphenol A epoxy resin 5 parts
5 parts of solvent;
the preparation method of the anti-welding ink based on the DCPD phenolic epoxy resin comprises the following steps of:
mixing the alkali-soluble epoxy acrylic resin, the UV monomer, the modified filler, the photoinitiator, the auxiliary agent and the solvent according to the parts by weight to obtain a component A; and (3) blending DCPD phenolic epoxy resin, bisphenol A epoxy resin 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 the product.
Example 2
A solder resist ink based on DCPD phenolic epoxy resin comprises an A component and a B component,
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 DCPD phenolic epoxy resin
Bisphenol A epoxy resin 10 parts
10 parts of solvent;
the preparation method of the anti-welding ink based on the DCPD phenolic epoxy resin comprises the following steps of:
mixing the alkali-soluble epoxy acrylic resin, the UV monomer, the modified filler, the photoinitiator, the auxiliary agent and the solvent according to the parts by weight to obtain a component A; and (3) blending DCPD phenolic epoxy resin, bisphenol A epoxy resin 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 the product.
Example 3
A solder resist ink based on DCPD phenolic epoxy resin comprises an A component and a B component,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
8 parts of DCPD phenolic epoxy resin
Bisphenol A epoxy resin 8 parts
8 parts of solvent;
the preparation method of the anti-welding ink based on the DCPD phenolic epoxy resin comprises the following steps of:
mixing the alkali-soluble epoxy acrylic resin, the UV monomer, the modified filler, the photoinitiator, the auxiliary agent and the solvent according to the parts by weight to obtain a component A; and (3) blending DCPD phenolic epoxy resin, bisphenol A epoxy resin 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 the product.
Comparative example 1
The comparative example differs from example 1 in that: the DCPD novolac epoxy resin was replaced with bisphenol a epoxy resin by equal mass, and the other components and preparation method were the same as in example 1.
Comparative example 2
The comparative example differs from example 1 in that: the modified filler was replaced with unmodified hexagonal boron nitride by equal mass, and the other components and the preparation method were the same as in example 1.
Comparative example 3
The comparative example differs from example 1 in that: the modified filler is replaced by polyethylene glycol modified hexagonal boron nitride, and in the preparation method of the modified filler, in the step S2, the trihydroxy polyoxypropylene ether is replaced by polyethylene glycol (purchased from Shanghai A Ding Shenghua technology Co., ltd., M) n =6000 g/mol), and the other components and preparation method are the same as in example 1.
Test case
The solder resist inks prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance test.
The test method is as follows:
adhesion test: the solder resist inks prepared in examples and comparative examples were applied to a PCB, respectively, and then photo-cured for 1h (wavelength 395nm,Intensity 25.0mW/cm 2 Is cured for 1 hour at 150 ℃ to form a film with a thickness of 0.5 mm. 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.
Stability test: the solder resist inks prepared in examples and comparative examples were each taken in 200mL of a sample, placed in a transparent container and sealed, left at room temperature for 30 days, and then observed for appearance, and evaluated on the following basis:
excellent: no sediment exists;
common: a small amount of precipitation;
poor: a large amount of precipitate.
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:
excellent: no or slight changes were found;
poor: the coating film is swelled or swelled and falls off.
Dielectric constant/dielectric loss test: a square-type cured ink test piece having a thickness of 100 μm and a size of 5 cm. Times.5 cm was prepared, and the test piece was sandwiched in a dielectric constant measuring instrument to measure the value of the center point.
Pencil hardness: measured based on JIS K5400.
Elongation rate: the elongation (elongation at break) of the film was measured by a tensile-compression tester (manufactured by Shimadzu corporation).
The test results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from table 1, the various properties of the DCPD novolac epoxy resin-based solder resist ink prepared in the embodiment of the invention are obviously superior to those of the comparative examples 1 to 3 in which the components are replaced, the DCPD novolac epoxy resin is replaced in the comparative example 1, the unmodified hexagonal boron nitride is replaced by the modified filler in the comparative example 2, and the polyethylene glycol modified hexagonal boron nitride is replaced by the modified filler in the comparative example 3, so that the compatibility between the components in the formulation is reduced, the synergistic effect is weakened, a more three-dimensional and stable structure is difficult to form, the mechanical properties are reduced, the dielectric constant and the dielectric loss are higher, and the ideal performance improvement cannot be realized. The anti-soldering ink based on the DCPD phenolic epoxy resin has good stability, acid and alkali resistance and mechanical property, and low dielectric constant and dielectric loss, and overcomes the defects in the prior art.
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 (7)
1. A DCPD phenolic epoxy resin-based solder resist ink is characterized in that the DCPD phenolic epoxy resin-based solder resist ink comprises an A component and a B component,
the component A comprises the following components in parts by weight:
30-60 parts of alkali-soluble epoxy acrylic resin
6-12 parts of UV monomer
3-8 parts of modified filler
1-3 parts of photoinitiator
1-6 parts of auxiliary agent
A solvent;
the component B comprises the following components in parts by weight:
1-10 parts of DCPD phenolic epoxy resin
Bisphenol A epoxy resin 1-10 parts
A solvent;
wherein,
the modified filler is trihydroxy polyoxypropylene ether modified hexagonal boron nitride;
the preparation method of the modified filler comprises the following steps:
s1, adding hexagonal boron nitride into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated hexagonal boron nitride;
s2, blending the carboxylated hexagonal boron nitride with an activating agent, adding trihydroxy polyoxypropylene ether, carrying out ultrasonic reaction, and purifying to obtain the modified filler;
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.
2. The DCPD novolac epoxy based solder mask ink of claim 1, wherein in step S1, the time of the ultrasonic treatment is 6-12h.
3. The DCPD novolac epoxy based solder mask ink of claim 1, wherein in step S2, the time of the ultrasonic reaction is 20-40h.
4. The DCPD novolac epoxy based solder resist ink according to claim 1, wherein in step S2, the mass ratio of carboxylated hexagonal boron nitride to trihydroxy polyoxypropylene ether is 1 (4-10).
5. The DCPD novolac epoxy resin based solder resist ink according to claim 1, wherein the activator is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine in a mass ratio of (2-6) 1.
6. The DCPD novolac epoxy based solder resist ink of claim 1, wherein the DCPD novolac epoxy resin has an epoxy equivalent weight of 250-300g/eq.
7. The method for preparing the DCPD-phenolic epoxy resin-based solder mask ink according to any one of claims 1 to 6, wherein the method for preparing the DCPD-phenolic epoxy resin-based solder mask ink comprises the following steps:
blending alkali-soluble epoxy acrylic resin, UV monomer, modified filler, photoinitiator, auxiliary agent and solvent to obtain a component A; and (3) blending DCPD phenolic epoxy resin, bisphenol A epoxy resin 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.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101278010A (en) * | 2005-10-07 | 2008-10-01 | 昭和电工株式会社 | Heat-curable resin composition including silicone powder |
| KR20100096675A (en) * | 2009-02-25 | 2010-09-02 | 주식회사 케이씨씨 | Solder resist composition comprising alkali developable modified acrylic copolymer |
| CN102786815A (en) * | 2012-08-15 | 2012-11-21 | 中国科学院上海硅酸盐研究所 | Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material |
| JP6061234B1 (en) * | 2016-03-11 | 2017-01-18 | 山栄化学株式会社 | Alkali development type solder resist ink, printed wiring board processing method and wiring board |
| CN107827770A (en) * | 2017-11-14 | 2018-03-23 | 西北工业大学 | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof |
| CN112445068A (en) * | 2019-09-02 | 2021-03-05 | 味之素株式会社 | Photosensitive resin composition |
| CN112812297A (en) * | 2021-01-21 | 2021-05-18 | 石家庄铁道大学 | Composite material, water-based anticorrosive wear-resistant paint, and preparation method and application thereof |
| CN113637338A (en) * | 2021-08-18 | 2021-11-12 | 天津大学 | Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof |
| CN114806269A (en) * | 2022-05-07 | 2022-07-29 | 佛山市西伦化工有限公司 | High-brightness liquid photosensitive solder mask ink and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63258975A (en) * | 1986-12-26 | 1988-10-26 | Toshiba Corp | Solder resist ink composition |
-
2023
- 2023-09-01 CN CN202311117996.XA patent/CN117126565B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101278010A (en) * | 2005-10-07 | 2008-10-01 | 昭和电工株式会社 | Heat-curable resin composition including silicone powder |
| KR20100096675A (en) * | 2009-02-25 | 2010-09-02 | 주식회사 케이씨씨 | Solder resist composition comprising alkali developable modified acrylic copolymer |
| CN102786815A (en) * | 2012-08-15 | 2012-11-21 | 中国科学院上海硅酸盐研究所 | Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material |
| JP6061234B1 (en) * | 2016-03-11 | 2017-01-18 | 山栄化学株式会社 | Alkali development type solder resist ink, printed wiring board processing method and wiring board |
| CN107827770A (en) * | 2017-11-14 | 2018-03-23 | 西北工业大学 | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof |
| CN112445068A (en) * | 2019-09-02 | 2021-03-05 | 味之素株式会社 | Photosensitive resin composition |
| CN112812297A (en) * | 2021-01-21 | 2021-05-18 | 石家庄铁道大学 | Composite material, water-based anticorrosive wear-resistant paint, and preparation method and application thereof |
| CN113637338A (en) * | 2021-08-18 | 2021-11-12 | 天津大学 | Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof |
| CN114806269A (en) * | 2022-05-07 | 2022-07-29 | 佛山市西伦化工有限公司 | High-brightness liquid photosensitive solder mask ink and preparation method thereof |
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