A kind of polybutadiene acrylic acid epoxy resin solder mask ink and preparation method thereof

Abstract

The present invention relates to a polybutadiene acrylic epoxy resin solder mask ink and a preparation method thereof, wherein the polybutadiene acrylic epoxy resin solder mask ink comprises component A and component B; component A comprises: 10-20 parts of polyester acrylic resin, 20-40 parts of active monomer, 10-30 parts of modified silica, 1-5 parts of glycidyl methacrylate, 1-10 parts of photoinitiator, and 1-10 parts of auxiliary agent; component B comprises: 20-40 parts of polybutadiene acrylic epoxy resin, wherein the modified silica is silane coupling agent, polyacrylic acid, and nonionic surfactant modified silica. The present invention adopts compounding of components such as polybutadiene acrylic epoxy resin, polyester acrylic resin, and modified silica, effectively improves the stability and adhesion of the solder mask ink, can meet the production needs of the industry, and has good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of solder resist ink, and in particular to a polybutadiene acrylic acid epoxy resin solder resist ink and a preparation method thereof. Background Art

[0002] Solder mask ink is an indispensable component of printed circuit boards. Solder mask ink covers the surface of electronic circuits and plays important functions such as moisture-proof, insulation, high temperature resistance and corrosion resistance. It is an important guarantee for the stable operation of electronic components.

[0003] Traditional solder mask inks have been widely used in the production of PCB boards. However, existing solder mask ink products still have many shortcomings, such as insufficient adhesion, which causes the ink to fall off easily and cannot effectively protect the circuit; uneven dispersion of components, resulting in an uneven ink surface and uneven color, which not only affects the subsequent process, but also reduces the appearance and image of the product; insufficient storage stability causes the ink to precipitate and stratify, affecting the use effect during printing, etc.

[0004] Today, as the performance of electronic products is developing rapidly, the requirements for the precision of electronic components are getting higher and higher, and the above-mentioned problems can no longer meet the current industry needs. Solder mask ink products also need to keep pace with the times, upgrade technology, and improve performance in all aspects to meet the development needs of the market and industry.

[0005] In summary, it is necessary to develop a new technical solution to solve the deficiencies in the prior art. Summary of the invention

[0006] Based on this, the present invention provides a polybutadiene acrylic epoxy resin solder mask ink and a preparation method thereof. The present invention uses a polybutadiene acrylic epoxy resin with multiple active functional groups, a polyester acrylic resin, modified silica and other components to effectively improve the stability, adhesion and other properties of the solder mask ink, can meet the production needs of the industry, and has good application prospects.

[0007] One object of the present invention is to provide a polybutadiene acrylic epoxy resin solder mask ink, wherein the polybutadiene acrylic epoxy resin solder mask ink comprises component A and component B;

[0008] The component A comprises the following components in parts by mass:

[0009]

[0010]

[0011] The component B comprises the following components in parts by weight:

[0012] Polybutadiene acrylic epoxy resin 20-40 parts

[0013] 10-20 parts of solvent;

[0014] in,

[0015] The modified silicon dioxide is silicon dioxide modified by a silane coupling agent, polyacrylic acid and a nonionic surfactant.

[0016] Furthermore, the nonionic surfactant is selected from one or more of oxyethylene ether / oxypropylene ether block polyether, fatty alcohol phosphate derivatives, ethoxylated fatty acid esters, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, and fatty acid polyoxyethylene esters.

[0017] Furthermore, the polyester acrylic resin is a carboxyl-containing polyester acrylic resin.

[0018] Furthermore, the carboxyl-containing polyester acrylic resin is selected from one or more of a copolymer of maleic anhydride and hydroxyethyl acrylate, a copolymer of epoxy acrylate and anhydride, and a carboxyl polyurethane acrylate.

[0019] Furthermore, the acid value of the carboxyl-containing polyester acrylic resin is 200 mgKOH / g.

[0020] Furthermore, the active monomer is a monomer having a monofunctional or multifunctional acrylate unit.

[0021] Furthermore, the auxiliary agent is selected from one or more of color powder, leveling agent, defoaming agent, ultraviolet absorber, dispersant, antioxidant and toughening agent.

[0022] Furthermore, the preparation method of the polybutadiene acrylic epoxy resin comprises the following steps:

[0023] Epoxy polybutadiene, acrylic acid, a catalyst and a polymerization inhibitor are mixed, heated at 50-100° C. with stirring for reaction for 3-6 hours, and polybutadiene acrylic epoxy resin is obtained after purification.

[0024] Another object of the present invention is to provide a method for preparing the polybutadiene acrylic acid epoxy resin solder mask ink, the method for preparing the polybutadiene acrylic acid epoxy resin solder mask ink comprising the following steps:

[0025] S1, mixing silicon dioxide and a silane coupling agent, heating and reacting to obtain an intermediate product;

[0026] S2, mixing the intermediate product, acrylic acid, a crosslinking agent and an initiator, heating the mixture under the protection of an inert gas for reaction, then adding a nonionic surfactant, and ultrasonically treating the mixture to obtain modified silicon dioxide;

[0027] S3. The modified silica, polyester acrylic resin, active monomer, glycidyl methacrylate, photoinitiator, auxiliary agent and solvent are mixed to obtain component A; polybutadiene acrylic epoxy resin and solvent are mixed to obtain component B, and the component A and component B are mixed, stirred and dispersed evenly, and then ground and filtered to obtain a product.

[0028] Furthermore, the silane coupling agent is an acrylate-based silane coupling agent.

[0029] Furthermore, in step S1, the heating reaction temperature is 30-60°C and the time is 12-36h.

[0030] Furthermore, in step S2, the heating reaction temperature is 60-80°C and the time is 12-36h.

[0031] Furthermore, in step S2, the ultrasonic treatment time is 1-6 hours.

[0032] The present invention has the following beneficial effects:

[0033] The polybutadiene acrylic epoxy resin solder mask ink provided by the present invention is obtained by compounding components such as polybutadiene acrylic epoxy resin, carboxyl-containing polyester acrylic resin, and modified silica. The modified silica is first treated with a silane coupling agent to introduce unsaturated double bonds on the surface, and then reacted with acrylic acid monomers to achieve the grafting of polyacrylic acid organic macromolecules, while introducing a large number of carboxyl groups, and finally adsorbed and cross-linked by intermolecular forces with alkoxy and hydroxyl groups in non-ionic surfactants to obtain modified silica with an outer layer of lipophilic segments. The modified silica of the present invention has good compatibility with organic polymers, can be wound through flexible carbon chains, is conducive to improving the toughness and strength of the ink, and has a large number of oxygen-containing active groups in the modified silica, can be adsorbed and combined with carboxyl-containing polyester acrylic resin through intermolecular forces, and can also be chemically cross-linked with polybutadiene acrylic epoxy resin to improve the cross-linking density, further promoting the improvement of ink stability and mechanical properties. Therefore, the present invention overcomes the deficiencies in the prior art and effectively improves product performance. DETAILED DESCRIPTION

[0034] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0035] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0036] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0037] The polybutadiene acrylic epoxy resin in the embodiment of the present invention is homemade, and the preparation method comprises the following steps:

[0038] Using ethyl acetate as solvent, epoxy polybutadiene, acrylic acid, triethylamine and hydroquinone in a mass ratio of 85:10:1:5 are mixed, stirred and reacted at 80° C. for 5 hours, and a prepolymer is separated. The prepolymer is then dissolved in toluene, and excess methanol is added for precipitation, and polybutadiene acrylic epoxy resin is separated and precipitated.

[0039] The epoxy polybutadiene in the embodiment of the present invention is purchased from Tianyuan Aerospace Materials Technology Co., Ltd.

[0040] The carboxyl-containing polyester acrylic resin in the embodiment of the present invention is a copolymer of acrylate and anhydride, with the brand name of Sartomer SB520A20 and an acid value of 200 mgKOH / g (content 80%).

[0041] The active monomers in the embodiment of the present invention are trimethylolpropane triacrylate (TMPTA) and polydipentaerythritol hexaacrylate (DPHA) in a mass ratio of 1:1.

[0042] The photoinitiators in the embodiments of the present invention are ITX and 819.

[0043] The auxiliary agent in the embodiment of the present invention is a leveling agent and a dispersant in a mass ratio of 1:1, the leveling agent is isopropanol, and the dispersant is sodium dodecyl sulfate.

[0044] The solvent in the embodiment of the present invention is dibasic acid ester (DBE).

[0045] The silicon dioxide in the embodiment of the present invention is subjected to surface activation pretreatment:

[0046] The silicon dioxide was immersed in a 5 wt % methanesulfonic acid aqueous solution, heated under reflux for 4 hours, and the product was obtained by filtering, washing and drying.

[0047] The "parts" in the embodiments of the present invention refer to parts by mass.

[0048] Example 1

[0049] A polybutadiene acrylic epoxy resin solder mask ink, comprising component A and component B;

[0050] The component A comprises the following components in parts by mass:

[0051]

[0052] The component B comprises the following components in parts by weight:

[0053] Polybutadiene acrylic epoxy resin 20 parts

[0054] 10 parts of solvent;

[0055] The preparation method of the polybutadiene acrylic acid epoxy resin solder mask ink comprises the following steps:

[0056] S1. Using ethanol and water in a volume ratio of 1:1 as solvent, adding silica and KH570 in a mass ratio of 1:1.5, reacting at 50°C for 24h, filtering, washing and drying to obtain an intermediate product;

[0057] S2, using water as solvent, mixing the intermediate product, methacrylic acid, N,N'-methylenebisacrylamide and ammonium persulfate in a mass ratio of 10:30:0.03:0.2, stirring and reacting at 70°C for 24 hours under nitrogen protection, filtering, washing and drying, mixing the solid product in a mass ratio of 1:5 with dodecylphenol polyoxyethylene ether, ultrasonically treating at 50°C for 5 hours, filtering and drying to obtain modified silicon dioxide;

[0058] S3. According to the above-mentioned mass fractions, the modified silica, polyester acrylic resin, active monomer, glycidyl methacrylate, photoinitiator, auxiliary agent and solvent are mixed to obtain component A; polybutadiene acrylic epoxy resin and solvent are mixed to obtain component B, and the components A and B are mixed, stirred and dispersed evenly, and then ground to a fineness of less than 1 μm to obtain a product.

[0059] Example 2

[0060] A polybutadiene acrylic epoxy resin solder mask ink, comprising component A and component B;

[0061] The component A comprises the following components in parts by mass:

[0062]

[0063] The component B comprises the following components in parts by weight:

[0064] Polybutadiene acrylic epoxy resin 30 parts

[0065] 15 parts of solvent;

[0066] The preparation method of the polybutadiene acrylic acid epoxy resin solder mask ink comprises the following steps:

[0067] S1. Using ethanol and water in a volume ratio of 1:1 as solvent, adding silica and KH570 in a mass ratio of 1:1.5, reacting at 50°C for 24h, filtering, washing and drying to obtain an intermediate product;

[0068] S2, using water as solvent, mixing the intermediate product, methacrylic acid, N,N'-methylenebisacrylamide and ammonium persulfate in a mass ratio of 10:30:0.03:0.2, stirring and reacting at 70°C for 24 hours under nitrogen protection, filtering, washing and drying, mixing the solid product in a mass ratio of 1:5 with dodecylphenol polyoxyethylene ether, ultrasonically treating at 50°C for 5 hours, filtering and drying to obtain modified silicon dioxide;

[0069] S3. According to the above-mentioned mass fractions, the modified dioxide, polyester acrylic resin, active monomer, glycidyl methacrylate, photoinitiator, auxiliary agent and solvent are mixed to obtain component A; polybutadiene acrylic epoxy resin and solvent are mixed to obtain component B, and the components A and B are mixed, stirred and dispersed evenly, and then ground to a fineness of less than 1 μm to obtain a product.

[0070] Example 3

[0071] A polybutadiene acrylic epoxy resin solder mask ink, comprising component A and component B;

[0072] The component A comprises the following components in parts by mass:

[0073]

[0074] The component B comprises the following components in parts by weight:

[0075] 40 parts of polybutadiene acrylic epoxy resin

[0076] 20 parts of solvent;

[0077] The preparation method of the polybutadiene acrylic acid epoxy resin solder mask ink comprises the following steps:

[0078] S1. Using ethanol and water in a volume ratio of 1:1 as solvent, adding silica and KH570 in a mass ratio of 1:1.5, reacting at 50°C for 24h, filtering, washing and drying to obtain an intermediate product;

[0079] S2, using water as solvent, mixing the intermediate product, methacrylic acid, N,N'-methylenebisacrylamide and ammonium persulfate in a mass ratio of 10:30:0.03:0.2, stirring and reacting at 70°C for 24 hours under nitrogen protection, filtering, washing and drying, mixing the solid product in a mass ratio of 1:5 with dodecylphenol polyoxyethylene ether, ultrasonically treating at 50°C for 5 hours, filtering and drying to obtain modified silicon dioxide;

[0080] S3. According to the above-mentioned mass fractions, the modified silica, polyester acrylic resin, active monomer, glycidyl methacrylate, photoinitiator, auxiliary agent and solvent are mixed to obtain component A; polybutadiene acrylic epoxy resin and solvent are mixed to obtain component B, and the components A and B are mixed, stirred and dispersed evenly, and then ground to a fineness of less than 1 μm to obtain a product.

[0081] Comparative Example 1

[0082] A polybutadiene acrylic epoxy resin solder mask ink. The difference between this comparative example and Example 1 is that the polybutadiene acrylic epoxy resin is replaced by E-44 epoxy resin, and the other ingredients and preparation method are the same as those in Example 1.

[0083] Comparative Example 2

[0084] A polybutadiene acrylic epoxy resin solder mask ink. The difference between this comparative example and Example 1 is that step S2 is modified as follows: using water as a solvent, mixing the intermediate product, methacrylic acid, N,N'-methylenebisacrylamide and ammonium persulfate in a mass ratio of 10:30:0.03:0.2, stirring and reacting at 70°C for 24 hours under nitrogen protection, filtering, washing and drying to obtain modified silicon dioxide. The other ingredients and preparation method are the same as those in Example 1.

[0085] Test Case

[0086] The performance of the polybutadiene acrylic epoxy resin solder mask ink prepared in Examples 1-3 and Comparative Examples 1-2 was tested.

[0087] The test method is as follows:

[0088] The polybutadiene acrylic epoxy resin solder mask ink prepared in the example and the comparative example was coated on the PCB board and light-cured for 1 h (wavelength 395 nm, intensity 25.0 mW / cm 2 The film was then cured at 150 °C for 1 h to form a 0.5 mm thick film.

[0089] Pencil hardness: measured in accordance with JIS K5400.

[0090] Adhesion: Use a needle tip to make an "X" on the film, then stick a cellophane tape on the cut and pull it, and evaluate based on the following criteria:

[0091] Good: no tearing or little tearing;

[0092] Poor: Extensive tear-off.

[0093] Acid resistance / alkali resistance: At 20°C, immerse the PCB coated with ink in a 10% sulfuric acid solution or a 10% sodium hydroxide solution, take it out after 30 minutes, and evaluate the state and adhesion of the coating. The judgment criteria are as follows:

[0094] Good: No changes or slight changes were found;

[0095] Poor: The coating film expands or swells and falls off.

[0096] Heat resistance: Thermal shock performance test is carried out according to the method in IPC-SM-840E, and the judgment criteria are as follows:

[0097] Good: no bubbles or cracks;

[0098] Poor: bubbles and cracks appear.

[0099] Bending resistance: With the solder mask film on the outside, bend it 180° and evaluate it based on the following criteria:

[0100] Good: No cracks on the film;

[0101] Poor: There are cracks on the film.

[0102] The test results are shown in Table 1.

[0103] Table 1 Performance test results

[0104]

[0105]

[0106] According to Table 1, it can be seen that the polybutadiene acrylic epoxy resin solder mask ink prepared in Examples 1-3 of the present invention has excellent adhesion, acid and alkali resistance and strength; Comparative Example 1 replaces the conventional epoxy resin with polybutadiene acrylic epoxy resin, which reduces the crosslinking density, and the synergistic effect between the components is small, which significantly reduces the adhesion and stability of the ink coating; Comparative Example 2 does not use a non-ionic surfactant to treat the silica, and the stability is also reduced, and the ideal performance improvement cannot be obtained. In summary, the polybutadiene acrylic epoxy resin solder mask ink of the present invention has obvious performance improvements and good application prospects.

[0107] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0108] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A polybutadiene acrylic epoxy resin solder mask ink, characterized in that: The polybutadiene acrylic epoxy resin solder mask ink comprises component A and component B; The component A comprises the following components in parts by mass: Polyester acrylic resin 10-20 parts Active monomer 20-40 parts Modified silica 10-30 parts Glycidyl methacrylate 1-5 parts Photoinitiator 1-10 parts 1-10 parts of additives 10-20 parts of solvent; The component B comprises the following components in parts by weight: Polybutadiene acrylic epoxy resin 20-40 parts 10-20 parts of solvent; in, The modified silica is silica modified by silane coupling agent, polyacrylic acid and nonionic surfactant; The polyester acrylic resin is a carboxyl-containing polyester acrylic resin; The silane coupling agent is an acrylate-based silane coupling agent; The preparation method of the polybutadiene acrylic acid epoxy resin solder mask ink comprises the following steps: S1, mixing silicon dioxide and a silane coupling agent, heating and reacting to obtain an intermediate product; S2, mixing the intermediate product, acrylic acid, a crosslinking agent and an initiator, heating the mixture under the protection of an inert gas for reaction, then adding a nonionic surfactant, and ultrasonically treating the mixture to obtain modified silicon dioxide; S3. The modified silica, polyester acrylic resin, active monomer, glycidyl methacrylate, photoinitiator, auxiliary agent and solvent are mixed to obtain component A; polybutadiene acrylic epoxy resin and solvent are mixed to obtain component B, and the component A and component B are mixed, stirred and dispersed evenly, and then ground and filtered to obtain a product.

2. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: The nonionic surfactant is selected from one or more of oxyethylene ether / oxypropylene ether block polyether, fatty alcohol phosphate derivatives, ethoxylated fatty acid esters, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, and fatty acid polyoxyethylene esters.

3. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: The reactive monomer is a monomer having a monofunctional or multifunctional acrylate unit.

4. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: The auxiliary agent is selected from one or more of color powder, leveling agent, defoamer, ultraviolet absorber, dispersant, antioxidant and toughening agent.

5. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: In step S1, the heating reaction temperature is 30-60°C and the time is 12-36 h.

6. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: In step S2, the heating reaction temperature is 60-80°C and the time is 12-36 hours.

7. The polybutadiene acrylic epoxy resin solder mask ink according to claim 1, characterized in that: In step S2, the ultrasonic treatment time is 1-6 h.

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