Unsaturated dibasic acid-modified alkali-soluble epoxy acrylate resin, its preparation method and application

Abstract

The present invention belongs to the technical field of polymer materials, and particularly relates to an alkali-soluble epoxy acrylate resin modified by an unsaturated dibasic acid, and a preparation method and application thereof. Calculated by mass parts, its raw material composition includes: 40-80 parts of unsaturated dibasic acid, 4-8 parts of catalyst, 1-4 parts of first inhibitor, 150-300 parts of first epoxy resin, 100-200 parts of second epoxy resin, 50-200 parts of monoisocyanate, 50-100 parts of unsaturated monobasic acid, 0.5-2 parts of second inhibitor, 100-300 parts of organic anhydride, and 300-500 parts of solvent. In the resin molecule of the present invention, there are multiple photocurable unsaturated groups at different sites and branched chains composed of epoxy resin, which have the advantages of high photosensitive curing activity, strong adhesion, fine development characteristics and low thermal expansion coefficient. Therefore, the photosensitive solder resist ink containing this resin has excellent properties such as photosensitivity, etching resistance, electroplating resistance, and film stripping property, and is suitable for application in the preparation of IC substrates and printed circuit boards.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to an unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin and a preparation method and application thereof. Background Art

[0002] IC substrate is a packaging method for high-frequency electronic chips. In the mid-1990s, a new type of IC high-density packaging represented by ball grid array packaging and chip size packaging came into being, and IC substrate came into being. It is developed on the basis of related technologies of printed circuit boards (PCBs) and is used to establish signal connections between ICs and PCBs. In addition, it can also protect circuits, fix lines and dissipate excess heat. In the field of high-frequency packaging, IC substrates have replaced traditional lead frames and become an indispensable part of chip packaging. They not only provide support, heat dissipation and protection for chips, but also provide electronic connections between chips and PCB motherboards, playing a "bridging" role.

[0003] Usually, a layer of solder resist coating is printed on the surface of PCB to play an insulating and protective role. The coating is formed by printing, photothermal curing, alkali washing and developing of alkali-soluble photosensitive resin. As a more advanced PCB board, the surface of IC carrier needs the protection of solder resist coating more, and the solder resist coating has strict photosensitivity, heat resistance, thermal expansion resistance, hardness, scratch resistance, impact resistance and other performance requirements. Even some applications require the solder resist coating to have a lower dielectric constant to meet high-frequency communication requirements. In short, IC carrier is directly involved in IC bare chip packaging. In order to ensure the working reliability of the packaged chip, various materials on the carrier, especially the performance reliability and dimensional precision of solder resist ink, have higher requirements. The prior art is still relatively lacking in IC carrier solder resist ink with excellent performance such as photosensitivity, etching resistance, electroplating resistance, and film fading. Therefore, it is necessary to improve the formula of solder resist ink and further improve its performance to meet the application requirements of IC carrier. Summary of the invention

[0004] The first object of the present invention is to provide an unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin. The second object of the present invention is to provide a method for preparing the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin. The third object of the present invention is to provide an application of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin.

[0005] According to the first aspect of the present invention, an alkali-soluble epoxy acrylic resin modified by an unsaturated dibasic acid is provided. The raw material composition thereof comprises, in parts by mass: 40-80 parts of an unsaturated dibasic acid, 4-8 parts of a catalyst, 1-4 parts of a first polymerization inhibitor, 150-300 parts of a first epoxy resin, 100-200 parts of a second epoxy resin, 50-200 parts of a monoisocyanate, 50-100 parts of an unsaturated monobasic acid, 0.5-2 parts of a second polymerization inhibitor, 100-300 parts of an organic acid anhydride, and 300-500 parts of a solvent.

[0006] In the present invention, the first epoxy resin is used as a base resin; the unsaturated dibasic acid can introduce unsaturated groups while extending the chain; the second epoxy resin can increase side chains to improve the shortcomings of the long-chain structure of the resin molecule; the monoisocyanate is used to cap and control the molecular weight of the resin to avoid gelation caused by unlimited reaction of epoxy groups and hydroxyl groups; the unsaturated monobasic acid is used to completely react the remaining epoxy groups to further increase the double bond content; the organic acid anhydride is used to improve the hydrophilicity of the resin and enable the resin to have alkaline development ability; the inhibitor is used to protect the double bonds from polymerization during the reaction; and the solvent is used to adjust the solid content and viscosity of the resin.

[0007] In some embodiments, the unsaturated dibasic acid is at least one of methylene succinic acid, butynedioic acid, hexamethylene dioic acid, glutamenedioic acid, and hexanedioic acid.

[0008] In some embodiments, the catalyst is at least one of benzyltriethylammonium chloride, triethylamine, triphenylphosphine, tetrabutylammonium bromide, and hexadecyltrimethylammonium bromide.

[0009] In some embodiments, the first inhibitor is at least one of hydroquinone, p-tert-butylcatechol, catechol, and p-hydroxyanisole.

[0010] In some embodiments, the first epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin.

[0011] In some embodiments, the second epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin.

[0012] In some embodiments, the monoisocyanate is at least one of tert-butyl isocyanate, n-butyl isocyanate, 3-propylene isocyanate, and triethoxypropyl isocyanate.

[0013] In some embodiments, the unsaturated monoacid is at least one of acrylic acid, crotonic acid, and propiolic acid.

[0014] In some embodiments, the second polymerization inhibitor is at least one of hydroquinone, p-tert-butylcatechol, catechol, and p-hydroxyanisole.

[0015] In some embodiments, the organic anhydride is at least one of maleic anhydride, succinic anhydride, 2-methylenesuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0016] In some embodiments, the solvent is a dibasic acid ester (DBE).

[0017] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin, comprising the following steps:

[0018] S1, mixing an unsaturated dibasic acid, a catalyst, a first polymerization inhibitor, and a first epoxy resin, heating to 90-100° C., and reacting until the acid value of the system drops below 3 mgKOH / g to obtain a semi-adduct of the unsaturated dibasic acid and the epoxy resin;

[0019] S2, mixing the second epoxy resin with the semi-adduct of the unsaturated dibasic acid and the epoxy resin obtained in step S1, heating to 130-150° C. for reaction for 3-6 hours, reacting until the epoxy equivalent of the system reaches the standard, cooling to 50-80° C., adding monoisocyanate, and reacting until the isocyanate group content is less than 3%, thereby obtaining a semi-adduct of the unsaturated dibasic acid and the epoxy resin terminated with monoisocyanate;

[0020] S3, heating the semi-adduct of the unsaturated dibasic acid terminated with a monoisocyanate and an epoxy resin obtained in step S2 to 60-90° C., adding an unsaturated monobasic acid and a second polymerization inhibitor, and then heating to 90-120° C., reacting until the acid value of the system is less than 3 mgKOH / g, to obtain an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0021] S4, cooling the unsaturated dibasic acid modified epoxy acrylic resin precursor obtained in step S3 to 60-70° C., adding organic acid anhydride and solvent, and then heating to 90-100° C., reacting until the acid value of the system reaches 30-50 mgKOH / g, and stopping the reaction to obtain the product.

[0022] The present invention firstly uses unsaturated dibasic acid containing olefins and alkynes to extend the chain of epoxy resin, then adds excess epoxy resin to react with hydroxyl groups generated by the previous reaction, monitors the change of epoxy equivalent of the system to control the reaction degree to reach the expected level, uses monoisocyanate to block, and then uses unsaturated monobasic acid to open the ring esterification of the remaining epoxy groups, so that the ends and the middle of the resin molecular chain have photocurable unsaturated groups such as olefins and alkynes at the same time, and the unsaturated groups at different sites can increase the cross-linking density of the resin molecules during photocuring, thereby improving the strength of the coating film, and at the same time, uses hydroxyl groups to introduce epoxy resin as a branch chain on the main chain of the resin, avoiding serious interchain entanglement and strong interaction of straight-chain polymer molecules, making the development boundary clearer and vertical, and effectively improving the development resolution, thermal expansion resistance, photosensitivity, etching resistance, electroplating resistance, film fading and other properties. Finally, the resin is modified by organic acid anhydride and carboxyl groups are introduced to make the resin have the ability of alkaline development.

[0023] The schematic diagram of the synthesis route of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of the present invention is as follows Figure 1 The first epoxy resin of the present invention is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin. 1 The structure of depends on the selection of the first epoxy resin, and is not listed one by one in the figure; the unsaturated dibasic acid is at least one of methylene succinic acid, butynedioic acid, hexenedioic acid, glutaric acid, and hexadienedioic acid. In the figure, the group R 2 The structure of is determined by the selection of the unsaturated dibasic acid, and is not listed one by one in the figure; the second epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin. In the figure, the group R 3 The structure of depends on the selection of the second epoxy resin, and is not listed one by one in the figure; the monoisocyanate is at least one of tert-butyl isocyanate, n-butyl isocyanate, 3-isocyanate propylene, and isocyanate propyltriethoxysilane. In the figure, the group R 4 The structure of depends on the selection of monoisocyanate, and is not listed one by one in the figure; the unsaturated monoacid is at least one of acrylic acid, crotonic acid, and propiolic acid. In the figure, the group R 5 The structure of depends on the selection of unsaturated monobasic acid, and is not listed one by one in the figure; the organic anhydride is at least one of maleic anhydride, succinic anhydride, 2-methylenesuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride. In the figure, the group R 6 The structure depends on the choice of organic anhydride and will not be listed one by one in the figure.

[0024] According to a third aspect of the present invention, there is provided a use of the above-mentioned unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin in the preparation of an IC carrier and / or a printed circuit board.

[0025] According to a fourth aspect of the present invention, a photosensitive solder resist ink is provided, wherein the raw material composition comprises, in terms of mass percentage, 40%-60% of the above-mentioned unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin, 1%-5% of a photoinitiator, 0.5%-5% of a pigment, 15%-40% of a filler, 10%-30% of an active diluent, 0.1-1% of a dispersant, 0.3-1% of a defoamer, 0.4-1% of a leveling agent, and 0.2-2% of a rheological additive.

[0026] In some embodiments, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-ethylanthraquinone, isopropylthioxanthone, 2,4-diethylthioxanthone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-difluoro-3-(1H-pyrrolyl-1)phenyl)titaniumocene, 9-anthracenemethyl N,N-diethylcarbamate, 2-(3-benzoylphenyl)guanidine propionate, and 1-(anthraquinone-2-yl)ethylimidazolecarboxylate.

[0027] In some embodiments, the pigment is at least one of phthalocyanine green, phthalocyanine blue, azo yellow, azo red, carbon black, and titanium dioxide.

[0028] In some embodiments, the filler is at least one of talc, barium sulfate, silica powder, kaolin, mica powder, and calcium carbonate.

[0029] In some embodiments, the reactive diluent is at least one of isobornyl acrylate, isobornyl methacrylate, ethoxyethoxyethyl acrylate, 2-phenoxyethyl acrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and ethoxylated trimethylolpropane triacrylate.

[0030] In some embodiments, the dispersant is BYK-154.

[0031] In some embodiments, the defoaming agent is BYK-071.

[0032] In some embodiments, the leveling agent is BYK-333.

[0033] In some embodiments, the rheology additive is BYK-431.

[0034] According to a fifth aspect of the present invention, there is provided a use of the above-mentioned photosensitive solder resist ink in the preparation of an IC substrate and / or a printed circuit board.

[0035] The beneficial effects of the present invention include:

[0036] The unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin of the present invention has a plurality of photocurable unsaturated groups and side chains composed of epoxy resin at different sites in the molecule, and has the advantages of high photocuring activity, strong adhesion, fine development characteristics and low thermal expansion coefficient. Therefore, the photosensitive solder resist ink containing the resin has excellent properties such as photosensitivity, etching resistance, electroplating resistance and film fading, and is suitable for use in the preparation of IC substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The schematic diagram is a synthetic route of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of the present invention. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below. It is worth noting that the following examples are only for better explanation of the present invention and are not intended to limit the scope of the present invention. The undisclosed process steps in the examples are prior art. Unless otherwise specified, the following raw materials are commercially available.

[0039] In the following examples, the stirring speed is 500 rpm.

[0040] Bisphenol A epoxy resin (NPEL-128) was purchased from Nanya Electronic Materials (Kunshan) Co., Ltd.

[0041] Dicyclopentadiene phenolic epoxy resin (DNE260H) was purchased from Changchun Artificial Resin Factory Co., Ltd.

[0042] The test methods for acid value, epoxy equivalent and isocyanate content are:

[0043] (1) Acid value test: Use potassium hydroxide standard solution to measure and calculate the acid value. The principle is: potassium hydroxide reacts with the remaining -COOH, KOH+RCOOH→H 2O+RCOOK. The specific operation is: add about 0.5g sample to a 100ml beaker, weigh accurately to 0.0002g, add about 20ml acetone, stir evenly with a glass rod until completely dissolved, if it cannot be dissolved at room temperature, heat appropriately; after complete dissolution, add 2-3 drops of 2% cresol red indicator, stir evenly, and titrate with about 0.2mol / L potassium hydroxide standard solution until the color changes from yellow to purple-red, and record the consumed volume (mL). The acid value (mg(KOH) / g) is calculated according to the following formula: Acid value (mg(KOH) / g) = V·C(KOH)×56.1 / G, where: V-consumed potassium hydroxide volume, mL; C-potassium hydroxide standard solution concentration, mol / L; G-sample weight, g.

[0044] (2) Epoxy equivalent test: The test is carried out in accordance with the national standard G "B / T 4612-2008 Determination of epoxy equivalent of plastic epoxy compounds".

[0045] (3) Isocyanate content test: The principle is to use isocyanate to react with excess di-n-butylamine to produce urea, and then use hydrochloric acid to titrate the excess di-n-butylamine to quantitatively calculate the isocyanate content, R-NCO+(C 4 H 9 ) 2 NH→RNHCON(C 4 H 9 ) 2 ;(C 4 H 9 ) 2 NH+HCl→(C 4 H 9 ) 2 NH·HCl. The specific operation is: first prepare the standard solution of bromocresol green indicator (0.1g bromocresol green is dissolved in 100mL of 20% ethanol solution by volume) and 0.1mol / L di-n-butylamine-toluene solution (dissolve 12.9g di-n-butylamine in toluene, transfer to a 1000mL volumetric flask, dilute to the mark with toluene, and shake well), then accurately weigh 1.0000g of sample into a dry conical flask, add 25ml toluene to dissolve the sample, accurately add 25.00mL di-n-butylamine-toluene solution, seal with a stopper, shake well, and let stand for 15min; then, add 100mL of isopropanol and 5 drops of bromocresol green indicator, and titrate with 0.1mol / L HCl standard solution to the end point (from blue to yellow). Perform a blank experiment at the same time. The isocyanate content is calculated as follows: W(NCO) / %=(V 0 -V)×c×4.202 / m, where: V 0-The volume of HCl standard solution consumed by the blank, mL; V-The volume of HCl standard solution consumed by the sample, mL; c-The concentration of HCl standard solution, mol / L; m-The mass of the sample, g.

[0046] Example 1

[0047] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0048] (1) 48.8 g of methylene succinic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0049] (2) 139.5 g of bisphenol A epoxy resin (NPEL-128) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out under vigorous stirring for about 4 hours. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 421 g / eq, the temperature was lowered to 60° C., 62.3 g of 3-isocyanatopropylene was added, and the reaction was completed after the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0050] (3) heating the system to 90° C., and dropwise adding a mixed solution of 81.1 g of acrylic acid and 0.61 g of p-hydroxyanisole into the above four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0051] (4) The system was cooled to 70° C., 171 g of tetrahydrophthalic anhydride and 425 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 42 mgKOH / g. The reaction was stopped to obtain the product.

[0052] Example 2

[0053] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0054] (1) 48.8 g of methylene succinic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0055] (2) 198.75 g of dicyclopentadiene novolac epoxy resin (DNE260H) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out under vigorous stirring for about 4 hours. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 475 g / eq, the temperature was lowered to 60° C., 62.3 g of 3-isocyanate propylene was added and the reaction was completed until the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0056] (3) heating the system to 90° C., and dropwise adding a mixed solution of 81.1 g of acrylic acid and 0.61 g of p-hydroxyanisole into the above four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0057] (4) The system was cooled to 70° C., 171 g of tetrahydrophthalic anhydride and 456 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 38 mgKOH / g. The reaction was stopped to obtain the product.

[0058] Example 3

[0059] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0060] (1) 42.77 g of butynedioic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0061] (2) 139.5 g of bisphenol A epoxy resin (NPEL-128) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out under vigorous stirring for about 4 hours. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 416 g / eq, the temperature was lowered to 60° C., 62.3 g of 3-isocyanate propylene was added, and the reaction was completed after the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0062] (3) heating the system to 90° C., and dropwise adding a mixed solution of 81.1 g of acrylic acid and 0.61 g of p-hydroxyanisole into the above four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0063] (4) The system was cooled to 70° C., 171 g of tetrahydrophthalic anhydride and 421 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 41 mgKOH / g. The reaction was stopped to obtain the product.

[0064] Example 4

[0065] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0066] (1) 48.8 g of methylene succinic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0067] (2) 139.5 g of bisphenol A epoxy resin (NPEL-128) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out for about 4 hours under vigorous stirring. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 421 g / eq, the temperature was lowered to 60° C., 185.52 g of isocyanatepropyltriethoxysilane was added, and the reaction was terminated after the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0068] (3) heating the system to 90° C., and dropwise adding a mixed solution of 81.1 g of acrylic acid and 0.61 g of p-hydroxyanisole into the above four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0069] (4) The system was cooled to 70° C., 171 g of tetrahydrophthalic anhydride and 492 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 35 mgKOH / g. The reaction was stopped to obtain the product.

[0070] Example 5

[0071] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0072] (1) 48.8 g of methylene succinic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0073] (2) 139.5 g of bisphenol A epoxy resin (NPEL-128) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out under vigorous stirring for about 4 hours. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 421 g / eq, the temperature was lowered to 60° C., 62.3 g of 3-isocyanatopropylene was added, and the reaction was completed after the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0074] (3) heating the system to 90° C., and dropwise adding a mixed solution of 96.85 g of crotonic acid and 0.61 g of p-hydroxyanisole into the four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0075] (4) The system was cooled to 70° C., 171 g of tetrahydrophthalic anhydride and 433 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 40 mgKOH / g. The reaction was stopped to obtain the product.

[0076] Example 6

[0077] The preparation method of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin of this embodiment comprises the following steps:

[0078] (1) 48.8 g of methylene succinic acid, 6.1 g of tetrabutylammonium bromide, 1.22 g of p-hydroxyanisole, and 279 g of bisphenol A epoxy resin (NPEL-128) were placed in a four-necked flask, nitrogen was connected, the system was heated to 100° C., and the system was reacted under vigorous stirring until the acid value of the system dropped to below 3 mgKOH / g, thereby obtaining a semi-adduct of an unsaturated dibasic acid and an epoxy resin;

[0079] (2) 139.5 g of bisphenol A epoxy resin (NPEL-128) was added to the above four-necked flask, the system was heated to 140° C., and the reaction was carried out under vigorous stirring for about 4 hours. The change of epoxy equivalent during the reaction was monitored. When the epoxy equivalent reached 421 g / eq, the temperature was lowered to 60° C., 62.3 g of 3-isocyanatopropylene was added, and the reaction was completed after the isocyanate content was less than 3%, thereby obtaining a semi-adduct of a monoisocyanate-terminated unsaturated dibasic acid and an epoxy resin;

[0080] (3) heating the system to 90° C., and dropwise adding a mixed solution of 81.1 g of acrylic acid and 0.61 g of p-hydroxyanisole into the above four-necked flask. After the dropwise addition, heating the system to 110° C., and reacting under vigorous stirring until the acid value of the system drops to below 3 mgKOH / g, thereby obtaining an unsaturated dibasic acid-modified epoxy acrylic resin precursor;

[0081] (4) The system was cooled to 70° C., 126.21 g of 2-methylenesuccinic anhydride and 400 g of dibasic solvent ester (DBE) were added to the above four-necked flask respectively, and then the system was heated to 100° C. and reacted under vigorous stirring until the acid value of the system dropped to 44 mgKOH / g. The reaction was stopped to obtain the product.

[0082] Next, the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin prepared in Examples 1-6 was used to prepare a photosensitive solder resist ink.

[0083] Application Example 1

[0084] The formulation of the photosensitive solder resist ink of this application example is shown in Table 1 below:

[0085] Table 1 Formulation of photosensitive solder resist ink

[0086]

[0087]

[0088] The preparation method thereof comprises the following steps:

[0089] The resin, photoinitiator, pigment, filler and dispersant are put into a dispersion barrel in proportion, and dispersed by a high-speed disperser at a rotation speed of about 1200 rpm for about 1.5 hours to uniformly mix the raw materials; then the dispersed raw materials are fully ground by a three-roll grinder to a fineness of 5 to 10 μm; then active diluent, leveling agent, defoaming agent and rheological additive are added to the ground raw materials, and dispersed by a high-speed disperser at a rotation speed of about 800 rpm for about 1.5 hours to uniformly mix the raw materials, and finally filtered to obtain the product.

[0090] Application Example 2

[0091] The formulation composition of the photosensitive solder resist ink of this application example is substantially the same as that of Table 1, except that the resin used is the unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin obtained in Example 2.

[0092] The preparation method is the same as that of Application Example 1.

[0093] Application Example 3

[0094] The formulation composition of the photosensitive solder resist ink of this application example is substantially the same as that of Table 1, except that the resin used is the unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin prepared in Example 3.

[0095] The preparation method is the same as that of Application Example 1.

[0096] Application Example 4

[0097] The formulation composition of the photosensitive solder resist ink of this application example is substantially the same as that of Table 1, except that the resin used is the unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin prepared in Example 4.

[0098] The preparation method is the same as that of Application Example 1.

[0099] Application Example 5

[0100] The formulation composition of the photosensitive solder resist ink of this application example is substantially the same as that of Table 1, except that the resin used is the unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin obtained in Example 5.

[0101] The preparation method is the same as that of Application Example 1.

[0102] Application Example 6

[0103] The formulation composition of the photosensitive solder resist ink of this application example is substantially the same as that of Table 1, except that the resin used is the unsaturated dibasic acid-modified alkali-soluble epoxy acrylic resin prepared in Example 6.

[0104] The preparation method is the same as that of Application Example 1.

[0105] Then, the performance of the photosensitive solder resist ink prepared in Example 1-6 was tested, and the testing method was as follows:

[0106] (1) Photosensitivity: Print the photosensitive solder resist ink on the copper clad laminate, bake it at 75°C for 20 minutes, place a 21-level light gradient ruler on the film layer, expose and develop it under an LED light source exposure machine, and use the time when 7 grids remain on the film layer as the standard.

[0107] (2) Minimum line spacing and line width: Tested in accordance with the method of GB / T 29846-2013 Photo-imaging electroplating resists for printed circuit boards.

[0108] (3) Etching resistance: The etching resistance is tested according to the method of GB / T 29846-2013 for photo-imaging electroplating resists for printed boards. After etching, the pattern is visually intact, the line edges are neat, and there is no wrinkling, shedding or dog-tooth shape. It is excellent. Wrinkling without shedding is good. Shedding is poor.

[0109] (4) Electroplating resistance: Electroplating resistance is tested according to the method of GB / T 29846-2013 Photo-imaging Electroplating Resist for Printed Boards. After electroplating, if the pattern has no seepage, bubbles, or shedding, it is excellent. If there is seepage but no shedding, it is good. If there is shedding, it is poor.

[0110] (5) Film fading property: The test specimens were placed in a 50°C, 3 wt% NaOH aqueous solution and the film fading performance was observed. The film fading performance was excellent if it completely shed within 60 seconds without any residue, good if it completely shed within 60-120 seconds without any residue, and poor if it shed after 120 seconds without any residue.

[0111] The test results are shown in Table 2.

[0112] Table 2 Performance test results of photosensitive solder resist inks of application examples 1-6

[0113]

[0114]

[0115] Photosensitivity: IC substrates generally require higher photosensitivity to ensure that the desired patterns and structures can be accurately formed during the exposure process. The test results in Table 1 show that the photosensitive solder resist ink of the present invention performs well in terms of photosensitivity, which means that it can be cured quickly and accurately during the exposure process, which is conducive to forming high-precision patterns and structures.

[0116] Etching resistance: IC substrates require high etching resistance to ensure that good pattern clarity and edge retention can be maintained during the etching process. The test results in Table 1 show that the photosensitive solder resist ink of the present invention has high etching resistance and can maintain pattern clarity and accuracy during the etching process.

[0117] Electroplating resistance: The IC substrate needs to have good electroplating resistance to ensure that the surface flatness and conductivity can be maintained during the electroplating process. The test results in Table 1 show that the photosensitive solder resist ink of the present invention has good electroplating resistance and can effectively prevent adverse reactions and defects during the electroplating process.

[0118] Film fading property: IC substrates require stable film fading properties to ensure that they can maintain stable performance and appearance for a long time during use. The test results in Table 1 show that the photosensitive solder resist ink of the present invention has excellent film fading properties, can maintain stable performance and appearance during long-term use, and meet the requirements of IC substrates.

[0119] Therefore, the photosensitive solder resist ink of the present invention has excellent properties such as photosensitivity, etching resistance, electroplating resistance, and film-fading resistance, and is suitable for use in preparing IC substrates and printed circuit boards.

[0120] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An alkali-soluble epoxy acrylic resin modified with an unsaturated dibasic acid, characterized in that: The raw material composition includes, by mass, 40-80 parts of unsaturated dibasic acid, 4-8 parts of catalyst, 1-4 parts of first polymerization inhibitor, 150-300 parts of first epoxy resin, 100-200 parts of second epoxy resin, 50-200 parts of monoisocyanate, 50-100 parts of unsaturated monobasic acid, 0.5-2 parts of second polymerization inhibitor, 100-300 parts of organic acid anhydride, and 300-500 parts of solvent; The preparation method thereof comprises the following steps: S1, mixing an unsaturated dibasic acid, a catalyst, a first polymerization inhibitor, and a first epoxy resin, heating to 90-100° C., and reacting until the acid value of the system drops below 3 mgKOH / g to obtain a semi-adduct of the unsaturated dibasic acid and the epoxy resin; S2, mixing the second epoxy resin with the semi-adduct of the unsaturated dibasic acid and the epoxy resin, heating to 130-150° C. for reaction for 3-6 hours, then cooling to 50-80° C., adding monoisocyanate, and reacting until the isocyanate group content is less than 3%, to obtain a semi-adduct of the unsaturated dibasic acid and the epoxy resin terminated with monoisocyanate; S3, heating the semi-adduct of the monoisocyanate-terminated unsaturated dibasic acid and epoxy resin to 60-90° C., adding the unsaturated monobasic acid and the second polymerization inhibitor, and then heating to 90-120° C., reacting until the acid value of the system is less than 3 mgKOH / g, to obtain an unsaturated dibasic acid-modified epoxy acrylic resin precursor; S4. Cool the unsaturated dibasic acid-modified epoxy acrylic resin precursor to 60-70°C, add organic acid anhydride and solvent, and then heat to 90-100°C. When the acid value of the system reaches 30-50 mgKOH / g, stop the reaction to obtain the product.

2. The unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to claim 1, characterized in that: The unsaturated dibasic acid is at least one of methylene succinic acid, butynedioic acid, hexamethylene dioic acid, glutamenedioic acid and hexanedioic acid.

3. The unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to claim 1 or 2, characterized in that: The catalyst is at least one of benzyltriethylammonium chloride, triethylamine, triphenylphosphine, tetrabutylammonium bromide, and hexadecyltrimethylammonium bromide; The first polymerization inhibitor is at least one of hydroquinone, p-tert-butylcatechol, catechol, and p-hydroxyanisole.

4. The unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to claim 1 or 2, characterized in that: The first epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin; The second epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene novolac epoxy resin, and alicyclic epoxy resin.

5. The unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to claim 1 or 2, characterized in that: The monoisocyanate is at least one of tert-butyl isocyanate, n-butyl isocyanate, 3-isocyanate propylene, and isocyanate propyltriethoxysilane; The unsaturated monoacid is at least one of acrylic acid, crotonic acid and propiolic acid; The second polymerization inhibitor is at least one of hydroquinone, p-tert-butylcatechol, catechol, and p-hydroxyanisole.

6. The unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to claim 1 or 2, characterized in that: The organic acid anhydride is at least one of maleic anhydride, succinic anhydride, 2-methylenesuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; The solvent is a divalent acid ester.

7. Use of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to any one of claims 1 to 6 in the preparation of IC substrates and / or printed circuit boards.

8. A photosensitive solder resist ink, characterized in that: The raw material composition comprises, in percentage by mass: 40%-60% of the unsaturated dibasic acid modified alkali-soluble epoxy acrylic resin according to any one of claims 1 to 6, 1%-5% of a photoinitiator, 0.5%-5% of a pigment, 15%-40% of a filler, 10%-30% of an active diluent, 0.1-1% of a dispersant, 0.3-1% of a defoamer, 0.4-1% of a leveling agent, and 0.2-2% of a rheological additive.

9. Use of the photosensitive solder resist ink according to claim 8 in the preparation of IC substrates and / or printed circuit boards.

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