CN117511292A - White solder resist ink and preparation method thereof - Google Patents
White solder resist ink and preparation method thereof Download PDFInfo
- Publication number
- CN117511292A CN117511292A CN202311410542.1A CN202311410542A CN117511292A CN 117511292 A CN117511292 A CN 117511292A CN 202311410542 A CN202311410542 A CN 202311410542A CN 117511292 A CN117511292 A CN 117511292A
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- Prior art keywords
- parts
- component
- solder resist
- stirring
- resist ink
- Prior art date
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 19
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- 239000000945 filler Substances 0.000 claims abstract description 88
- 239000002904 solvent Substances 0.000 claims abstract description 55
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 49
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 48
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 23
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 23
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- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 93
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- 238000006243 chemical reaction Methods 0.000 claims description 65
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 55
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- 150000002989 phenols Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 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
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 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
- 238000002310 reflectometry Methods 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
- 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
- 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
- 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a white solder resist ink and a preparation method thereof, wherein the white solder resist ink comprises a component A and a component B; wherein the component A comprises the following components in parts by weight: 10-50 parts of alkali-soluble hydrogenated bisphenol A epoxy resin, 1-10 parts of active monomer, 1-10 parts of modified filler 1, 1-10 parts of modified filler 2, 1-10 parts of photoinitiator and 10-50 parts of solvent; the component B comprises the following components in parts by weight: 1-10 parts of hydrogenated bisphenol A epoxy resin, 1-10 parts of auxiliary agent and 1-10 parts of solvent; wherein the modified filler 1 is carboxymethyl cellulose and polyethyleneimine grafted inorganic filler; the modified filler 2 is hyperbranched polyglycidyl ether grafted inorganic filler. The components of the invention can produce synergistic effect, thus not only improving the yellowing resistance of the white ink, but also endowing the product with stronger mechanical property and stability and overcoming the defects in the prior art.
Description
Technical Field
The invention relates to the technical field of solder resist ink, in particular to white solder resist ink and a preparation method thereof.
Background
White solder resist ink is a key raw material for producing LED circuit boards. The solder resist reflective coating of the circuit board is formed after exposure imaging curing, so that solder is prevented from damaging copper wires, and the light reflectivity of the circuit board is improved, thereby ensuring the yield of the circuit board and increasing the brightness of a lamp light source.
With the application and development of high-end LED products such as MiniLED, the requirements on yellowing resistance of photosensitive solder resist white oil of a printed circuit board are higher and higher. The traditional white solder resist ink generally uses common epoxy resin and epoxy acrylate containing benzene rings as main body resins, and has the defect of poor yellowing resistance. In the process of reflow soldering and lamp use, unsaturated benzene rings can be oxidized due to high temperature and ultraviolet irradiation to generate chromophore groups, so that resin denaturation, yellowing of white coating and light reflectivity drop are caused.
The prior art adopts the technical proposal that acrylic ester copolymer with epoxy groups is grafted with acrylic acid to introduce photosensitive group double bonds, and finally grafted with anhydride to introduce carboxyl groups of alkali developable groups. The alkali developable resin with the acrylate structure is an aliphatic acrylic epoxy resin, and is not easy to generate a chromophoric group under ultraviolet rays or high temperature, so that the yellowing resistance effect is more excellent than that of the traditional product. However, acrylic materials are generally brittle, have large volume shrinkage, and are generally poor in solvent and chemical resistance. Therefore, how to provide a white solder resist ink with strong yellowing resistance, high chemical resistance and high mechanical property 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 white solder resist ink and a preparation method thereof. According to the invention, alkali-soluble hydrogenated bisphenol A epoxy resin is adopted as a main resin, and two modified fillers are adopted as components, wherein the modified filler 1 is carboxymethyl cellulose and polyethylene imine grafted inorganic filler, and the modified filler 2 is hyperbranched polyglycidyl ether grafted inorganic filler, so that polyethylene imine, carboxymethyl cellulose macromolecules and hyperbranched alkoxy chain segments are introduced into the surface of the inorganic filler, so that the epoxy resin has stronger dispersibility and compatibility, and can generate a synergistic effect with other components, the yellowing resistance of white ink is improved, the stronger mechanical property and stability of the product are simultaneously endowed, and the defects in the prior art are overcome.
An object of the present invention is to provide a white solder resist ink including an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
1-10 parts of auxiliary agent
1-10 parts of a solvent;
wherein,
the modified filler 1 is carboxymethyl cellulose and polyethyleneimine grafted inorganic filler;
the modified filler 2 is hyperbranched polyglycidyl ether grafted inorganic filler.
Further, the reactive monomer is a monomer having a monofunctional or polyfunctional acrylate unit.
Further, the auxiliary agent is selected from one or more of toner, flatting agent, defoamer, ultraviolet absorber, dispersant, antioxidant and flexibilizer.
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.
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: a series of anionic surfactants 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 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.
Another object of the present invention is to provide a method for preparing the white solder resist ink, which includes the following steps:
s1, adding inorganic filler into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated filler;
s2, dispersing the carboxylated filler in water to obtain a dispersion liquid, then adding polyethyleneimine and potassium hydroxide, and heating and stirring to react to obtain an intermediate product;
Adding carboxymethyl cellulose into the intermediate product, stirring, adding epichlorohydrin, heating for reaction, and purifying to obtain modified filler 1;
s3, mixing glycerol and sodium methoxide, stirring, heating for reaction, then adding a solvent under vacuum condition, heating, stirring, adding glycidol, preserving heat, and purifying to obtain hyperbranched polyglycidyl ether;
blending the carboxylated filler with an activating agent, adding hyperbranched polyglycidyl ether, and carrying out ultrasonic reaction to obtain modified filler 2;
s4, blending alkali-soluble hydrogenated bisphenol A epoxy resin, an active monomer, modified filler 1, modified filler 2, a photoinitiator and a solvent to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, grinding and filtering to obtain a product.
Further, in the step S2, the temperature of the heating and stirring reaction is 80-90 ℃ and the time is 10-20 hours; the temperature of the heating reaction is 80-90 ℃ and the time is 10-20h.
Further, in the step S2, the mass ratio of the carboxylated filler to the polyethyleneimine to the potassium hydroxide to the carboxymethyl cellulose to the epichlorohydrin is (0.1-0.5) to (1-5) to (0.1-1) to (1-5).
Further, in the step S3, 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 hyperbranched polyglycidyl ether is 1 (4-10), and the time of the ultrasonic reaction is 20-40h.
Further, the activators are 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (edc.hcl) and 4-Dimethylaminopyridine (DMAP).
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, 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 an inorganic filler was added, and the mixture was sonicated at 50℃for 8 hours (power: 500W), and the product was washed with deionized water and ethanol to neutrality, and then dried at 60℃overnight to give a carboxylated filler.
Further, step S2 includes the steps of:
adding carboxylated filler into deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding polyethylenimine and potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
Adding carboxymethyl cellulose into the intermediate product, stirring for 1h, adding epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1.
Further, step S3 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 hyperbranched polyglycidyl ether is obtained;
and (2) taking N, N-dimethylformamide as a solvent, blending the carboxylated filler with activating agents EDC, HCl and DMAP, stirring for 0.5h, adding the hyperbranched polyglycidyl ether (carboxylated filler: hyperbranched 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 modified filler 2.
Another object of the present invention is to provide an application of the above white solder resist ink in a PCB substrate.
The invention has the following beneficial effects:
the white solder resist ink provided by the invention adopts an alkali-soluble hydrogenated bisphenol A epoxy resin main resin and is compounded with two modified fillers. Wherein, the hydrogenated bisphenol A epoxy resin not only maintains the excellent chemical resistance and solvent resistance of the epoxy resin system, but also solves the problem that the white ink is easy to yellow because of not containing benzene rings. In the modified inorganic filler, firstly, carboxylation treatment is carried out on the filler, polyethyleneimine is introduced into the modified filler 1 through the reaction of carboxyl and amino on the surface of the filler, and then amidation reaction is carried out on the amino in the polyethyleneimine and carboxyl in carboxymethyl cellulose, so that carboxymethyl cellulose molecules are further grafted, and the hardness and strength of the ink coating are obviously improved; the modified filler 2 is prepared from glycerin, sodium methoxide and glycidol serving as raw materials to prepare hyperbranched polyglycidyl ether, and then hydroxyl groups in the hyperbranched polyglycidyl ether react with carboxyl groups on the surface of the filler, so that an alkoxy chain segment with a branched structure is introduced. The two modified fillers have better dispersibility, avoid aggregation and uneven dispersion of a large number of fillers, and simultaneously, because a large number of amino, hydroxyl, carboxyl and other active groups are introduced on the surface of the fillers, the fillers are easier to crosslink with organic components such as resin and the like to form a reticular structure, thereby generating a synergistic effect, effectively improving the compatibility among components and improving the mechanical property of the ink; hydrogen bonds can also be generated between reactive functional groups that are not crosslinked, further enhancing the stability of the ink product and coating by intermolecular forces. Therefore, the invention solves the defects in the prior art and has good application prospect.
Drawings
Figure 1 shows an optical microscope picture of the white ink prepared in example 1,
wherein,
FIG. 1 (a) shows the line coverage of a white ink;
fig. 1 (b) shows the bottom side etching of the white ink.
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 preparation method of the alkali-soluble hydrogenated bisphenol A epoxy resin in the embodiment of the invention comprises the following steps:
adding 500 parts of hydrogenated bisphenol A epoxy resin and 180 parts of acrylic acid into 300 parts of diethylene glycol monoethyl ether acetate, heating to 100 ℃, stirring, and dissolving until uniformity; 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 hydrogenated bisphenol A epoxy resin is obtained.
The hydrogenated bisphenol A epoxy resin in the embodiment of the invention is purchased from complex high new materials (Shanghai) limited company, and has the brand of HE4080E and the viscosity of 2300cps@25deg.C; the epoxy equivalent weight is 210-230g/eq.
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 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 titanium dioxide, 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).
Boron nitride in the examples of the present invention was purchased from ala Ding Shiji limited and had an analytically pure purity.
The polyethyleneimine of the examples of the present invention was purchased from Shanghai Ala Biotechnology Co., ltd, and had a molecular weight of about 600g/mol.
The carboxymethyl cellulose in the examples of the present invention was purchased from Tianjin far chemical reagent Co., ltd, and the purity was analytically pure.
In the embodiment of the invention, "parts" refer to parts by weight.
Example 1
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary 1 part
2 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
S4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary agent 5 parts
10 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
Adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary 2 parts
4 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
Mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 4
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary agent 3 parts
6 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
S4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 5
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary agent 4 parts
8 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
Adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 6
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary 2 parts
3 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
Mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 7
A white solder resist ink comprising an a-component and a B-component;
wherein,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
hydrogenated bisphenol A epoxy resin 5 parts
Auxiliary agent 3 parts
5 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
S4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 8
A white solder resist ink comprising an a-component and a B-component;
wherein,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
7 parts of hydrogenated bisphenol A epoxy resin
Auxiliary agent 4 parts
7 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
Adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 9
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary 2 parts
2 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
Mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
s4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 10
A white solder resist ink comprising an a-component and a B-component;
wherein,
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 hydrogenated bisphenol A epoxy resin
Auxiliary agent 10 parts
10 parts of solvent;
the preparation method of the white solder resist 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, adding 1g of carboxylated boron nitride into 14mL of deionized water, performing ultrasonic dispersion for 30min to obtain a dispersion liquid, then stirring at 80 ℃ for 1h, adding 40g of polyethyleneimine and 1.5g of potassium hydroxide, and stirring at 80 ℃ for reacting for 12h to obtain an intermediate product;
adding 10g of carboxymethyl cellulose into the intermediate product, stirring for 1h, adding 50g of epichlorohydrin, reacting at 80 ℃ for 12h, centrifuging, washing, and freeze-drying to obtain modified filler 1;
s3, 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 hyperbranched polyglycidyl ether is obtained;
mixing carboxylated boron nitride with activating agents EDC, HCl and DMAP by taking N, N-dimethylformamide as a solvent, stirring for 0.5h, adding hyperbranched polyglycidyl ether (carboxylated boron nitride, hyperbranched 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 modified filler 2;
S4, blending the modified filler 1, the modified filler 2, the alkali-soluble hydrogenated bisphenol A epoxy resin, the active monomer, the photoinitiator and the solvent according to the parts by weight to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, 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 difference between this comparative example and example 1 is that: step S2 is omitted, and in step S4, the modified filler 1 is replaced with unmodified boron nitride by equal mass, and other components and preparation methods are the same as those of example 1.
Comparative example 2
The difference between this comparative example and example 1 is that: step S3 is omitted, and in step S4, the modified filler 2 is replaced with unmodified boron nitride by equal mass, and other components and preparation methods are the same as in example 1.
Comparative example 3
The difference between this comparative example and example 1 is that: in step S4, the alkali-soluble hydrogenated bisphenol A epoxy resin and the hydrogenated bisphenol A epoxy resin were replaced with bisphenol A epoxy resin (NPEL-128, nanya resin Co., ltd.) and the other components and the preparation method were the same as in example 1.
Test case
The white 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:
the solder resist inks prepared in examples and comparative examples were applied to a PCB, respectively, and photo-cured for 1h (wavelength 395nm, intensity 25.0mW/cm 2 Is then thermally cured at 150℃for 1 hour to form a film of 0.5mm thickness.
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;
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.
Elongation rate: the elongation (elongation at break) of the film was measured by a tensile-compression tester (manufactured by Shimadzu corporation).
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 performed according to the method in IPC-SM-840E, and the criterion was as follows:
qualified: no bubbles or cracks;
disqualification: air bubbles and cracking occur.
Cold and hot cycle impact:
firstly, pretreatment is carried out: after 24 hours at 125 ℃, the mixture was left at 60 ℃ and 60% RH for 52 hours; then, cold and hot condition circulation is carried out: after 15min at-65 ℃, 15min at 150 ℃ again, the cycle is performed, the conversion time is less than 10s, and the cycle times are 1000 times. The decision criteria are as follows:
qualified: the cracking, falling and other conditions are avoided;
disqualification: cracking and falling off occur.
Anti-yellowing properties: and measuring the reflectivity of the sample after three times of reflow soldering, wherein the reflow soldering rod part is as follows: 160 ℃ +180 ℃ +200 ℃ +220 ℃ +240 ℃ +265 ℃ +240 ℃ +200 ℃, for 8 temperature zones, 300s.
The test results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from Table 1, the white solder resist ink prepared in the examples of the present invention has various properties significantly superior to those of comparative examples 1 to 3, and comparative examples 1 to 2 replace the modified filler, resulting in a decrease in dispersibility and compatibility of the components and a significant decrease in mechanical properties; whereas comparative example 3 replaced hydrogenated bisphenol a epoxy resin, resulting in reduced stability of the ink coating and poor anti-yellowing properties.
Figure 1 shows an optical microscope picture of the white ink prepared in example 1,
wherein,
FIG. 1 (a) shows the line coverage of a white ink;
fig. 1 (b) shows the bottom side etching of the white ink.
As can be seen from fig. 1, the white ink prepared according to the present invention has excellent line coverage ability and less undercut.
In conclusion, the white solder resist ink disclosed by the invention keeps good mechanical strength, greatly improves the yellowing resistance, overcomes the defects in the prior art, and has 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 (10)
1. A white solder resist ink, wherein the white solder resist ink comprises an a component and a B component;
wherein,
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 hydrogenated bisphenol A epoxy resin
1-10 parts of auxiliary agent
1-10 parts of a solvent;
wherein,
the modified filler 1 is carboxymethyl cellulose and polyethyleneimine grafted inorganic filler;
the modified filler 2 is hyperbranched polyglycidyl ether grafted inorganic filler.
2. The white solder resist ink of claim 1, wherein the reactive monomer is a monomer having a monofunctional or polyfunctional acrylate unit.
3. The white solder resist ink of claim 1, wherein said auxiliary agent is selected from one or more of a toner, a leveling agent, a defoamer, an ultraviolet absorber, a dispersant, an antioxidant, and a toughening agent.
4. The white solder resist ink of claim 1, wherein said inorganic filler is selected from one or more of silica, carbonate, sulfate, talc, mica powder, silica micropowder, kaolin, wollastonite, metal oxide, metal hydroxide, carbon nanotubes, boron nitride, and graphene.
5. The method for preparing the white solder resist ink according to any one of claims 1 to 4, wherein the method for preparing the white solder resist ink comprises the following steps:
s1, adding inorganic filler into a strong acid solution, performing ultrasonic treatment, and purifying to obtain carboxylated filler;
s2, dispersing the carboxylated filler in water to obtain a dispersion liquid, then adding polyethyleneimine and potassium hydroxide, and heating and stirring to react to obtain an intermediate product;
adding carboxymethyl cellulose into the intermediate product, stirring, adding epichlorohydrin, heating for reaction, and purifying to obtain modified filler 1;
s3, mixing glycerol and sodium methoxide, stirring, heating for reaction, then adding a solvent under vacuum condition, heating, stirring, adding glycidol, preserving heat, and purifying to obtain hyperbranched polyglycidyl ether;
blending the carboxylated filler with an activating agent, adding hyperbranched polyglycidyl ether, and carrying out ultrasonic reaction to obtain modified filler 2;
s4, blending alkali-soluble hydrogenated bisphenol A epoxy resin, an active monomer, modified filler 1, modified filler 2, a photoinitiator and a solvent to obtain a component A; mixing hydrogenated bisphenol A epoxy resin, an auxiliary agent and a solvent to obtain a component B, mixing the component A and the component B, stirring and dispersing uniformly, grinding and filtering to obtain a product.
6. The method for preparing white solder resist ink according to claim 5, wherein in step S2, the temperature of the heating and stirring reaction is 80-90 ℃ for 10-20 hours; the temperature of the heating reaction is 80-90 ℃ and the time is 10-20h.
7. The method for preparing white solder resist ink according to claim 5, wherein in step S2, the mass ratio of the carboxylated filler, the polyethylenimine, the potassium hydroxide, the carboxymethyl cellulose and the epichlorohydrin is (0.1-0.5): 1-5): 0.1-1): 1-5.
8. The method for preparing white solder resist ink according to claim 5, wherein in step S3, the temperature of the stirring and heating reaction is 30-60 ℃ for 1-3 hours; 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.
9. The method for preparing white solder resist ink according to claim 5, wherein in the step S3, the mass ratio of the carboxylated filler to the hyperbranched polyglycidyl ether is 1 (4-10), and the time of the ultrasonic reaction is 20-40 hours.
10. Use of the white solder resist ink of any of claims 1-4 in a PCB substrate.
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