Low-loss circuit board ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, in particular to low-loss circuit board ink and a preparation method thereof.Urethane acrylate is selected as main light-cured resin, polymethyl methacrylate is introduced to serve as a raw material, dicyclopentadiene-phenol epoxy resin serves as a hardening agent, and silica powder serves as filler; the preparation method comprises the following steps: synthesizing a prepolymer by using hydroxyl-terminated polybutadiene as a raw material and isophorone diisocyanate under the action of a catalyst, and synthesizing composite polyurethane acrylate by using hydroxyethyl acrylate and a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer as end-capping reagents; the silica powder is firstly carboxylated, and then the hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer is used for modification treatment, so that the adhesive force of the silica powder is improved, the problems of falling and the like of the silica powder under the conditions of external force impact and the like are prevented, and various properties of the ink are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and specifically to a low-loss circuit board ink and a preparation method thereof. Background Art

[0002] A printed circuit board is a substrate for connecting and installing various microelectronic devices. With the advent of the 5G era, the requirement for the signal transmission speed is getting higher and higher, and the requirement for the signal integrity of the printed circuit board is also increasing.

[0003] In the manufacturing process of printed circuit boards, solder mask inks are usually printed on their surfaces to avoid welding damage. Therefore, the performance of the solder mask ink will directly affect the yield of the subsequent installed devices, thus affecting the reliability of the printed circuit board. At the same time, the heat resistance, water resistance, and corrosion resistance of the solder mask ink are also closely related to the service life of the printed circuit board. Summary of the Invention

[0004] The purpose of the present invention is to provide a low-loss circuit board ink and a preparation method thereof to solve the problems in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions: A preparation method of a low-loss circuit board ink, comprising the following steps: S1: Mix and stir polymethyl methacrylate, composite polyurethane acrylate, reactive diluent, modified silica powder, photoinitiator, and solvent, grind and sieve to obtain a mixed base material A; S2: Mix and stir dicyclopentadiene-phenol epoxy resin, additives, and pigments, grind and sieve to obtain a mixed base material B; S3: Put the mixed base material A and the mixed base material B into a high-speed disperser for dispersion treatment to obtain a low-loss circuit board ink.

[0006] Further, the working conditions of the dispersion treatment are: the temperature is 55-65°C, and the time is 1-2h.

[0007] Further, the additives are obtained by compounding a dispersant, a leveling agent, and an antifoaming agent in a mass ratio of 1:1:1.

[0008] Further, the reactive diluent is one or a combination of bis-trimethylolpropane tetraacrylate, dipropylene glycol diacrylate, and trimethylolpropane triacrylate.

[0009] Further, the mass ratio of the mixed base material A to the mixed base material B is 85:15.

[0010] Further, based on parts by weight, the raw material composition of the mixed base material A is as follows: 11-16 parts of polymethyl methacrylate, 22-42 parts of composite polyurethane acrylate, 1-3 parts of active diluent, 1-3 parts of photoinitiator, 4-9 parts of modified silica powder, and 10-20 parts of solvent.

[0011] Further, in the mixed base material B, the mass ratio of dicyclopentadiene-phenol epoxy resin, auxiliary agent, and pigment is 10:2:3.

[0012] Further, the preparation of the composite polyurethane acrylate includes the following steps: Under a nitrogen atmosphere, keep the hydroxyl-terminated polybutadiene in an oil bath at 105 °C for 2 h, cool it to 18-25 °C, add ethyl acetate, add a mixed solution of isophorone diisocyanate and ethyl acetate, add dibutyltin dilaurate and p-methoxyphenol, keep it in an oil bath at 38-42 °C for 30-40 min, add a mixed solution of hydroxyethyl acrylate, hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer, and ethyl acetate, add dibutyltin dilaurate and p-methoxyphenol, raise the temperature to 68-72 °C and keep it for 1-2 h to obtain the composite polyurethane acrylate.

[0013] Further, the preparation of the modified silica powder includes the following steps: The preparation of the modified silica powder includes the following steps: (1) Mix 3-aminopropyltriethoxysilane, succinic anhydride, and N,N-dimethylformamide, stir for 2-3 h, raise the temperature to 50-60 °C, add a mixed solution of silica powder and N,N-dimethylformamide, add deionized water, continue to stir for 4-5 h, centrifuge, wash with alcohol, and dry to obtain carboxylated silica powder; (2) Under a nitrogen atmosphere, mix the hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer, carboxylated silica powder, p-toluenesulfonic acid, and N,N-dimethylformamide, keep it at 140-145 °C for 4-5 h, cool, filter by suction, wash, and dry to obtain the modified silica powder.

[0014] Further, the preparation of the hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer includes the following steps: 1) Under a nitrogen atmosphere, mix 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 4,4'-difluorobenzophenone, potassium carbonate, N-methylpyrrolidone, and toluene, raise the temperature to 148-152 °C and keep it for 1 h, then raise the temperature to 178-182 °C and keep it for 2-3 h, cool to 18-25 °C, add propargyl bromide, raise the temperature to 58-62 °C and keep it for 23-24 h, wash with hot water, filter, dry, add chloroform, and add ethanol to obtain a poly(aryl ether ketone) oligomer with an alkyne group at the end; 2) Mix isopropanol and epoxy-terminated polydimethylsiloxane, add deionized water and sodium azide, adjust the pH value of the solution to 5, stir overnight at 45 - 50 °C, adjust the pH value of the solution to 7, extract with pentane 3 - 4 times, wash and dry to obtain azide-terminated polydimethylsiloxane; 3) Under a nitrogen atmosphere, mix an alkyne-terminated polyaryletherketone oligomer, azide-terminated polydimethylsiloxane, N-methylpyrrolidone, and tetrahydrofuran, add copper sulfate and sodium ascorbate, raise the temperature to 58 - 62 °C and hold for 7 - 8 h, pour into ethanol, dry, place in a Soxhlet extractor, extract with acetone as the extractant, and dry to obtain a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a low-loss circuit board ink and its preparation method, and a highly reliable solder resist ink with good high-temperature resistance, strong corrosion resistance, and good hydrophobicity is prepared. When it is applied to the surface solder resist process of printed circuit boards such as high multi-layer high-density packaging printed boards, arbitrary interconnection boards, and server boards, it has characteristics such as high stability and low dielectric loss.

[0016] In the present invention, polyurethane acrylate, which combines the excellent flexibility of polyurethane and the excellent weather resistance and chemical reagent resistance of acrylate, is selected as the main photocurable resin, polymethyl methacrylate is introduced as a raw material, dicyclopentadiene-phenol epoxy resin is used as a hardener, and silica powder is used as a filler. Under the action of an initiator, an ink cured by both light and heat is prepared to improve the performance of the ink.

[0017] To further improve the high-temperature resistance of the ink, the present invention selects hydroxyl-terminated polybutadiene with a flexible long carbon chain structure as a raw material, synthesizes a prepolymer with isophorone diisocyanate under the action of a catalyst, and uses 2-hydroxyethyl acrylate and a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer as capping agents to synthesize a photocurable composite polyurethane acrylate with good mechanical strength, resistance to high and low temperatures, and hydrophobicity; the hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer is prepared from phthalazinone biphenyl bisphenol and difluoro ketone as raw materials, and undergoes nucleophilic polycondensation and propargyl bromide capping in sequence to obtain an alkyne-terminated polyaryletherketone oligomer at the end of the molecular chain, and then is prepared by click grafting azide-terminated polydimethylsiloxane, thereby greatly improving the high and low temperature resistance and hydrophobicity of the ink.

[0018] To improve the uniformity of the dispersion of the filler silica powder in the ink, the silica powder is first carboxylated, and then modified with a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer to improve the adhesion of the silica powder and prevent problems such as the silica powder falling off under conditions such as external force impact, thereby improving the high-temperature resistance, water resistance, and corrosion resistance of the ink. Detailed implementation mode

[0019] The following will describe the technical solutions in the present invention clearly and completely in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0020] It should be noted that if there are directional indications such as up, down, left, right, front, and back in the embodiments of the present invention, the directional indications are only used to explain the relative position relationship and movement conditions between components in a specific posture. If the specific posture changes, the directional indications will also change accordingly. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement it. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0021] The following further describes the technical solutions of the present invention in detail in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0022] Embodiment 1: A preparation method of a low-loss circuit board ink, comprising the following steps: S1: Stir and mix polymethyl methacrylate, composite polyurethane acrylate, active diluent, modified silica powder, photoinitiator, and solvent in a mixer, grind and screen to obtain a mixed base material A; By weight, the raw material composition of the mixed base material A is: 11 parts of polymethyl methacrylate, 22 parts of composite polyurethane acrylate, 1 part of active diluent, 1 part of photoinitiator, 4 parts of modified silica powder, and 10 parts of solvent; The preparation of the composite polyurethane acrylate includes the following steps: Under a nitrogen atmosphere, keep 3 g of hydroxyl-terminated polybutadiene in an oil bath at 105 °C for 2 h, cool to 18 °C, add 3 g of ethyl acetate, add a mixture of 0.4 g of isophorone diisocyanate and 1 g of ethyl acetate, add 1.67 mg of dibutyltin dilaurate and 3.4 mg of p-hydroxyanisole, keep in an oil bath at 38 °C for 40 min, add a mixture of 0.2 g of hydroxyethyl acrylate, 0.3 g of a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer, and 1 g of ethyl acetate, add 3 mg of dibutyltin dilaurate and 4 mg of p-hydroxyanisole, raise the temperature to 68 °C and keep for 2 h to obtain the composite polyurethane acrylate; The preparation of the modified silica powder includes the following steps: (1) Mix 1 mmol of 3-aminopropyltriethoxysilane, 1 mmol of succinic anhydride, and 20 mL of N,N-dimethylformamide, stir for 2 h, heat up to 50 °C, add a mixture of 2 g of silica powder and 18 mL of N,N-dimethylformamide, add 2 mL of deionized water, continue to stir for 4 h, centrifuge, wash with alcohol, and dry to obtain carboxylated silica powder; (2) Under a nitrogen atmosphere, mix 2.8 g of hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer, 1.6 g of carboxylated silica powder, 0.1 g of p-toluenesulfonic acid, and 50 mL of N,N-dimethylformamide, keep warm at 140 °C for 5 h, cool, filter, wash, and dry to obtain modified silica powder; The preparation of the hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer includes the following steps: 1) Under a nitrogen atmosphere, mix 2.4 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 1.6 g of 4,4'-difluorobenzophenone, 1.7 g of potassium carbonate, 15 mL of N,N-dimethylformamide, and 2 mL of toluene, heat up to 148 °C and keep warm for 1 h, then heat up to 182 °C and keep warm for 2 h, cool down to 18 °C, add 1.2 g of propargyl bromide, heat up to 58 °C and keep warm for 23 h, wash with hot water, filter, dry, add chloroform, and add ethanol to obtain a poly(aryl ether ketone) oligomer with an alkyne group at the end; 2) Mix 80 mL of isopropanol and 2.4 g of epoxy-terminated polydimethylsiloxane, add 15 mL of deionized water and 1.04 g of sodium azide, adjust the pH value of the solution to 5, stir overnight at 45 °C, adjust the pH value of the solution to 7, extract 3 times with 30 mL of pentane, wash and dry to obtain azidopolydimethylsiloxane; 3) Under a nitrogen atmosphere, mix 0.5 g of the poly(aryl ether ketone) oligomer with an alkyne group at the end, 1.5 g of azidopolydimethylsiloxane, 7.5 mL of N-methylpyrrolidone, and 7.5 mL of tetrahydrofuran, add 0.02 g of copper sulfate and 0.03 g of sodium ascorbate, heat up to 58 °C and keep warm for 8 h, pour into ethanol, dry, place in a Soxhlet extractor, extract with acetone as the extractant, and dry to obtain a hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer; The active diluent is dipropylene glycol diacrylate; S2: Stir and mix dicyclopentadiene-phenol epoxy resin, additives, and pigments, grind and sieve to obtain mixed base material B; In mixed base material B, the mass ratio of dicyclopentadiene-phenol epoxy resin, additives, and pigments is 10:2:3; The additives are obtained by compounding a dispersant, a leveling agent, and an antifoaming agent in a mass ratio of 1:1:1; S3: Put the mixed base material A and the mixed base material B into a high-speed disperser for dispersion treatment to obtain a low-loss circuit board ink; the mass ratio of the mixed base material A to the mixed base material B is 85:15; the working conditions for the dispersion treatment are: the temperature is 55°C and the time is 2 h.

[0023] Example 2: A preparation method of a low-loss circuit board ink, comprising the following steps: S1: Stir and mix polymethyl methacrylate, composite polyurethane acrylate, active diluent, modified silica powder, photoinitiator, and solvent in a mixer, grind and sieve to obtain the mixed base material A; By weight, the raw material composition of the mixed base material A is: 13 parts of polymethyl methacrylate, 31 parts of composite polyurethane acrylate, 2 parts of active diluent, 2 parts of photoinitiator, 6 parts of modified silica powder, and 15 parts of solvent; The preparation of the composite polyurethane acrylate comprises the following steps: Under a nitrogen atmosphere, keep 3 g of hydroxyl-terminated polybutadiene in an oil bath at 105°C for 2 h, cool to 20°C, add 3 g of ethyl acetate, add a mixture of 0.4 g of isophorone diisocyanate and 1 g of ethyl acetate, add 1.67 mg of dibutyltin dilaurate and 3.4 mg of p-hydroxyanisole, keep in an oil bath at 40°C for 35 min, add a mixture of 0.2 g of hydroxyethyl acrylate, 0.3 g of hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer, and 1 g of ethyl acetate, add 3 mg of dibutyltin dilaurate and 4 mg of p-hydroxyanisole, raise the temperature to 70°C and keep for 1.5 h to obtain the composite polyurethane acrylate; The preparation of the modified silica powder comprises the following steps: (1) Mix 1 mmol of 3-aminopropyltriethoxysilane, 1 mmol of succinic anhydride, and 20 mL of N,N-dimethylformamide, stir for 2.5 h, raise the temperature to 55°C, add a mixture of 2 g of silica powder and 18 mL of N,N-dimethylformamide, add 2 mL of deionized water, continue to stir for 4.5 h, centrifuge, wash with alcohol, and dry to obtain carboxylated silica powder; (2) Under a nitrogen atmosphere, mix 2.8 g of hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer, 1.6 g of carboxylated silica powder, 0.1 g of p-toluenesulfonic acid, and 50 mL of N,N-dimethylformamide, keep at 143°C for 4.5 h, cool, filter, wash, and dry to obtain the modified silica powder; The preparation of the hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer comprises the following steps: 1) Under a nitrogen atmosphere, 2.4 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 1.6 g of 4,4'-difluorobenzophenone, 1.7 g of potassium carbonate, 15 mL of N,N-dimethylformamide, and 2 mL of toluene were mixed. The temperature was raised to 150 °C and maintained for 1 h, then raised to 180 °C and maintained for 2.5 h. After cooling to 20 °C, 1.2 g of propargyl bromide was added, and the temperature was raised to 60 °C and maintained for 23.5 h. After washing with hot water, filtering, and drying, chloroform was added, and then ethanol was added to obtain a polyaryletherketone oligomer with an alkynyl group at the end; 2) 80 mL of isopropanol and 2.4 g of epoxy-terminated polydimethylsiloxane were mixed, 15 mL of deionized water and 1.04 g of sodium azide were added, the pH value of the solution was adjusted to 5, and the mixture was stirred overnight at 48 °C. Then the pH value of the solution was adjusted to 7, and it was extracted 3 times with 30 mL of pentane, washed, and dried to obtain azidopolydimethylsiloxane; 3) Under a nitrogen atmosphere, 0.5 g of the polyaryletherketone oligomer with an alkynyl group at the end, 1.5 g of azidopolydimethylsiloxane, 7.5 mL of N-methylpyrrolidone, and 7.5 mL of tetrahydrofuran were mixed. 0.02 g of copper sulfate and 0.03 g of sodium ascorbate were added, and the temperature was raised to 60 °C and maintained for 7.5 h. Then it was poured into ethanol, dried, placed in a Soxhlet extractor, extracted with acetone as the extractant, and dried to obtain a polyaryletherketone-polydimethylsiloxane copolymer containing hydroxyl groups; The active diluent is dipropylene glycol diacrylate; S2: Dicyclopentadiene-phenol epoxy resin, additives, and pigments were stirred and mixed, ground and sieved to obtain a mixed base material B; In the mixed base material B, the mass ratio of dicyclopentadiene-phenol epoxy resin, additives, and pigments is 10:2:3; The additives are obtained by compounding a dispersant, a leveling agent, and an antifoaming agent in a mass ratio of 1:1:1; S3: The mixed base material A and the mixed base material B were put into a high-speed disperser for dispersion treatment to obtain a low-loss circuit board ink; the mass ratio of the mixed base material A to the mixed base material B is 85:15; the working conditions for the dispersion treatment are: temperature 60 °C, time 1.5 h.

[0024] Example 3: A preparation method of a low-loss circuit board ink, comprising the following steps: S1: Poly(methyl methacrylate), composite polyurethane acrylate, active diluent, modified silica powder, photoinitiator, and solvent were stirred and mixed in a mixer, ground and sieved to obtain a mixed base material A; By weight, the raw material composition of the mixed base material A is: 16 parts of poly(methyl methacrylate), 42 parts of composite polyurethane acrylate, 3 parts of active diluent, 3 parts of photoinitiator, 9 parts of modified silica powder, and 20 parts of solvent; The preparation of the composite polyurethane acrylate comprises the following steps: Under a nitrogen atmosphere, 3 g of hydroxyl-terminated polybutadiene is kept warm in an oil bath at 105 °C for 2 h, cooled to 25 °C, 3 g of ethyl acetate is added, a mixed solution of 0.4 g of isophorone diisocyanate and 1 g of ethyl acetate is added, 1.67 mg of dibutyltin dilaurate and 3.4 mg of p-hydroxyanisole are added, kept warm in an oil bath at 42 °C for 30 min, a mixed solution of 0.2 g of hydroxyethyl acrylate, 0.3 g of hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer and 1 g of ethyl acetate is added, 3 mg of dibutyltin dilaurate and 4 mg of p-hydroxyanisole are added, the temperature is raised to 72 °C and kept warm for 1 h to obtain the composite polyurethane acrylate; The preparation of the modified silica powder comprises the following steps: (1) 1 mmol of 3-aminopropyltriethoxysilane, 1 mmol of succinic anhydride and 20 mL of N,N-dimethylformamide are mixed, stirred for 3 h, the temperature is raised to 60 °C, a mixed solution of 2 g of silica powder and 18 mL of N,N-dimethylformamide is added, 2 mL of deionized water is added, stirring is continued for 5 h, centrifuged, washed with alcohol and dried to obtain carboxylated silica powder; (2) Under a nitrogen atmosphere, 2.8 g of hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer, 1.6 g of carboxylated silica powder, 0.1 g of p-toluenesulfonic acid and 50 mL of N,N-dimethylformamide are mixed, kept warm at 145 °C for 4 h, cooled, filtered by suction, washed and dried to obtain the modified silica powder; The preparation of the hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer comprises the following steps: 1) Under a nitrogen atmosphere, 2.4 g of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one, 1.6 g of 4,4'-difluorobenzophenone, 1.7 g of potassium carbonate, 15 mL of N,N-dimethylformamide and 2 mL of toluene are mixed, the temperature is raised to 152 °C and kept warm for 1 h, then the temperature is raised to 182 °C and kept warm for 2 h, cooled to 25 °C, 1.2 g of propargyl bromide is added, the temperature is raised to 62 °C and kept warm for 23 h, washed with hot water, filtered and dried, chloroform is added, and ethanol is added to obtain a poly(aryl ether ketone) oligomer with an alkyne group at the end; 2) Mixed with 80 mL of isopropanol and 2.4 g of epoxy-terminated polydimethylsiloxane, 15 mL of deionized water and 1.04 g of sodium azide are added, the pH value of the solution is adjusted to 5, stirred overnight at 50 °C, the pH value of the solution is adjusted to 7, extracted 4 times with 30 mL of pentane, washed and dried to obtain azidopoly(dimethylsiloxane); 3) Under a nitrogen atmosphere, 0.5 g of an alkyne-terminated polyaryletherketone oligomer, 1.5 g of azidopolysiloxane, 7.5 mL of N-methylpyrrolidone, and 7.5 mL of tetrahydrofuran were mixed. 0.02 g of copper sulfate and 0.03 g of sodium ascorbate were added. The temperature was raised to 62 °C and kept for 7 h, then poured into ethanol, dried, placed in a Soxhlet extractor, extracted with acetone as the extractant, and dried to obtain a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer; The active diluent is dipropylene glycol diacrylate; S2: Dicyclopentadiene-phenol epoxy resin, additives, and pigments were stirred and mixed, ground and sieved to obtain a mixed base material B; In the mixed base material B, the mass ratio of dicyclopentadiene-phenol epoxy resin, additives, and pigments is 10:2:3; The additives are obtained by compounding a dispersant, a leveling agent, and an antifoaming agent in a mass ratio of 1:1:1; S3: The mixed base material A and the mixed base material B were put into a high-speed disperser for dispersion treatment to obtain a low-loss circuit board ink; the mass ratio of the mixed base material A to the mixed base material B is 85:15; the working conditions for the dispersion treatment are: the temperature is 65 °C and the time is 1 h.

[0025] Comparative Example 1: Using Example 3 as a control group, polyurethane acrylate (000000380: Wuhan Karnos Technology Co., Ltd.) was used to replace the composite polyurethane acrylate, and other processes were normal.

[0026] Comparative Example 2: Using Example 3 as a control group, silica powder was used to replace the modified silica powder, and other processes were normal.

[0027] In the examples and comparative examples, the solvent is a mixture of tetrahydrofuran and n-hexane in a mass ratio of 1:1.

[0028] Sources of raw materials used (for demonstration only): Silica powder (average particle size 0.39 µm, density 2.23 g / cm 3, Dk(1MHz) is 3.82, Df(1MHz) is 0.00019): commercially available; photoinitiator (2-hydroxy-2-methylpropiophenone, 99%) from Shanghai Tongyuan Chemical Co., Ltd.; hydroxyl-terminated polybutadiene 0002 from Wuhan Pulov Bio-Technology Co., Ltd.; dicyclopentadiene-phenol epoxy resin HP-7200 from Guangzhou Taiji New Materials Co., Ltd.; dispersant CP-88 from Linyi Guoli Chemical Industry Co., Ltd.; leveling agent TSF400 from Guangzhou Hengyu Chemical Industry Co., Ltd.; defoaming agent XPJ05 from Jinan Shanhaiguan Chemical Technology Co., Ltd.; pigment (green) GA3274 from Hubei Guangao Bio-Technology Co., Ltd.; p-methoxyphenol (industrial grade) from Hubei Qifei Pharmaceutical and Chemical Co., Ltd.; 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (industrial grade) from Dalian Baolimo New Materials Co., Ltd.; epoxy-terminated polydimethylsiloxane 2315 from Suzhou Senfeida Chemical Co., Ltd.; 3-aminopropyltriethoxysilane A107147, succinic anhydride S104823, p-toluenesulfonic acid T104290, isophorone diisocyanate I109582, polymethyl methacrylate P742581, dibutyltin dilaurate D100274, 2-hydroxyethyl acrylate H104535, 4,4'-difluorobenzophenone M106424, propargyl bromide P106961, sodium ascorbate S105024, dipropylene glycol diacrylate D154720: from Aladdin Reagent; ethyl acetate, isopropanol, potassium carbonate, toluene, chloroform, N,N-dimethylformamide, ethanol, sodium azide, N-methylpyrrolidone, tetrahydrofuran, copper sulfate pentahydrate, n-hexane, pentane, analytical grade: commercially available.

[0029] Performance testing: The inks prepared in the examples and comparative examples were tested: The inks prepared in the examples and comparative examples were coated on a 1.5 oz copper plate at 60 µm, kept at 75 °C for 60 min, and irradiated at 500 mj / cm 2 for 60 s to obtain specimens; Hydrophobicity: characterized by water contact angle and tested with a tester using 2 µL of deionized water as the test liquid; high temperature resistance: tested by a hot and cold cycle method. The specimen was kept at a high temperature of 260 °C for 15 s, taken out and then kept at a low temperature of -10 °C for 15 s. After 10 high and low temperature cycles, if there were no phenomena such as air bubbles, peeling, or breakage in the ink layer, it was qualified; otherwise, it was unqualified; corrosion resistance: The specimen was placed in a 10% mass concentration sodium chloride aqueous solution and kept at 26 °C for 26 h. If there were no phenomena such as air bubbles, peeling, or breakage in the ink layer, it was qualified; otherwise, it was unqualified; The obtained results are shown in Table 1; Table 1

[0030] The present invention provides a low-loss circuit board ink and a preparation method thereof, and a highly reliable solder resist ink with good high-temperature resistance, strong corrosion resistance and good hydrophobicity is prepared. When it is applied to the surface solder resist process of printed circuit boards such as high multi-layer high-density packaging printed boards, arbitrary interconnection boards, server boards, etc., it has characteristics such as high stability and low dielectric loss.

[0031] Comparing Example 3 with Comparative Example 1, it can be seen that in order to further improve the high-temperature resistance of the ink, the present invention selects hydroxyl-terminated polybutadiene with a flexible long carbon chain structure as a raw material to synthesize a prepolymer with isophorone diisocyanate under the action of a catalyst, and uses 2-hydroxyethyl acrylate and a hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer as a capping agent to synthesize a photocurable composite polyurethane acrylate with good mechanical strength, high and low temperature resistance and hydrophobicity; the hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer is prepared from phthalazinone biphenyl bisphenol and difluoro ketone as raw materials, and successively undergoes nucleophilic polycondensation and bromopropynyl capping to obtain a poly(aryl ether ketone) oligomer with an alkyne group at the molecular chain end, and then is prepared by click grafting azidopoly(dimethylsiloxane), so as to obtain a hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer, thereby greatly improving the high and low temperature resistance and hydrophobicity of the ink.

[0032] Comparing Example 3 with Comparative Example 2, it can be seen that in order to improve the uniformity of the dispersion of the filler silica powder in the ink, the silica powder is first carboxylated, and then modified with a hydroxyl-containing poly(aryl ether ketone)-polydimethylsiloxane copolymer to improve the adhesion of the silica powder and prevent problems such as the silica powder falling off under conditions such as external force impact, thereby improving the high-temperature resistance, water resistance and corrosion resistance of the ink.

[0033] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. All equivalent structural transformations made using the specification of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for preparing low-loss circuit board ink, characterized in that: The following steps are involved: S1: polymethyl methacrylate, composite polyurethane acrylate, reactive diluent, modified silica powder, photoinitiator and solvent are stirred and mixed, and then ground and sieved to obtain a mixed base material A; S2: mixing dicyclopentadiene-phenol epoxy resin, additives and pigments, grinding and sieving to obtain a mixed base material B; S3: Put the mixed base material A and the mixed base material B into a high-speed disperser for dispersion treatment to obtain a low-loss circuit board ink.

2. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The working conditions of the dispersion treatment are: temperature 55-65°C, time 1-2h.

3. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The auxiliary agent is a dispersant, a leveling agent and a defoaming agent mixed in a mass ratio of 1:1:

1.

4. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The active diluent is one or a combination of ditrimethylolpropane acrylate, dipropylene glycol diacrylate, and propane trimethanol triacrylate.

5. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The mass ratio of the mixed base material A to the mixed base material B is 85:

15.

6. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: In terms of weight, the raw material composition of the mixed base material A is: 11-16 parts of polymethyl methacrylate, 22-42 parts of composite polyurethane acrylate, 1-3 parts of active diluent, 1-3 parts of photoinitiator, 4-9 parts of modified silicon micropowder, and 10-20 parts of solvent; in the mixed base material B, the mass ratio of dicyclopentadiene-phenol epoxy resin, additives, and pigment is 10:2:

3.

7. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The preparation of the composite polyurethane acrylate comprises the following steps: Under a nitrogen atmosphere, the terminal hydroxyl polybutadiene is kept in an oil bath at 105°C for 2 hours, cooled to 18-25°C, ethyl acetate is added, a mixture of isophorone diisocyanate and ethyl acetate is added, dibutyltin dilaurate and p-hydroxyanisole are added, and the mixture is kept in an oil bath at 38-42°C for 30-40 minutes, hydroxyethyl acrylate, a mixture of hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer and ethyl acetate are added, dibutyltin dilaurate and p-hydroxyanisole are added, the temperature is raised to 68-72°C and kept for 1-2 hours to obtain a composite polyurethane acrylate.

8. The method for preparing a low-loss circuit board ink according to claim 1, characterized in that: The preparation of the modified silicon micropowder comprises the following steps: (1) 3-aminopropyltriethoxysilane, succinic anhydride and N,N-dimethylformamide are mixed and stirred for 2-3 hours, the temperature is raised to 50-60°C, a mixed solution of silicon micropowder and N,N-dimethylformamide is added, deionized water is added, stirring is continued for 4-5 hours, centrifuged, washed with alcohol, and dried to obtain carboxylated silicon micropowder; (2) In a nitrogen atmosphere, a hydroxyl-containing polyaryletherketone-polydimethylsiloxane copolymer, carboxylated silicon micropowder, p-toluenesulfonic acid, and N,N-dimethylformamide are mixed, kept at 140-145°C for 4-5 hours, cooled, filtered, washed, and dried to obtain modified silicon micropowder.

9. The method for preparing a low-loss circuit board ink according to claim 7 or 8, characterized in that: The preparation of the hydroxy-containing polyaryletherketone-polydimethylsiloxane copolymer comprises the following steps: 1) Under nitrogen atmosphere, 4-(4-hydroxyphenyl)-2,3-naphthyridin-1-one, 4,4'-difluorobenzophenone, potassium carbonate, N-methylpyrrolidone and toluene are mixed, heated to 148-152°C and kept for 1 hour, heated to 178-182°C and kept for 2-3 hours, cooled to 18-25°C, propargyl bromide is added, heated to 58-62°C and kept for 23-24 hours, washed with hot water, filtered, dried, added with chloroform, and added with ethanol to obtain a polyaryletherketone oligomer containing an alkynyl group at the end; 2) Mix isopropanol and epoxy-terminated polydimethylsiloxane, add deionized water and sodium azide, adjust the pH value of the solution to 5, stir at 45-50° C. overnight, adjust the pH value of the solution to 7, extract with pentane 3-4 times, wash and dry to obtain azid polydimethylsiloxane; 3) Under a nitrogen atmosphere, a poly(aryl ether ketone) oligomer containing an alkynyl group at the end, poly(dimethylsiloxane) azide, N-methylpyrrolidone and tetrahydrofuran are mixed, copper sulfate and sodium ascorbate are added, the temperature is raised to 58-62°C and kept warm for 7-8 hours, poured into ethanol, dried, placed in a Soxhlet extractor, extracted with acetone as an extractant, and dried to obtain a hydroxyl-containing poly(aryl ether ketone)-poly(dimethylsiloxane) copolymer.

10. A low-loss circuit board ink, characterized in that: The method is prepared according to any one of claims 1 to 8.

Images