Electroplating-resistant chemical-plating-resistant black solder resist ink and preparation method thereof

Abstract

The invention discloses an electroplating-resistant chemical-plating-resistant black solder resist ink and a preparation method thereof, and belongs to the technical field of solder resist inks, the electroplating-resistant chemical-plating-resistant black solder resist ink comprises a component A and a component B, the component A comprises the following components: matrix resin, a photoinitiator, carbon black, a filler, a solvent, a fluorine-containing leveling agent, a defoaming agent and a dispersing agent; the component B is prepared from the following components: a diluent, novolac epoxy resin, triglycidyl isocyanurate, poly [(2-oxiranyl)-1, 2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1, 3-propylene glycol ether, a silane coupling agent and a solvent; the black solder resist ink disclosed by the invention has excellent electroplating resistance and chemical plating resistance effects, can effectively reduce the printing thickness, enables black which is difficult to expose to have a good exposure effect, has good resolution and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of solder resist ink technology, specifically to an anti-electroplating and anti-chemical plating black solder resist ink and its preparation method. Background Technology

[0002] Solder resist ink is mainly used on printed circuit boards (PCBs). To prevent unnecessary solder from adhering to the PCB during soldering and causing short circuits, a layer of solder resist ink needs to be printed on the circuit lines. Depending on the application, solder resist ink comes in different colors, including green, blue, white, and black. Black solder resist ink, in addition to providing a more aesthetically pleasing and high-end texture, also provides full coverage, ensuring that the protected circuit pattern is not directly visible. In many applications, it is necessary to electroplate copper-tin, nickel-tin, or electroless nickel-gold to thicken the conductive layer and improve solder resistance, requiring the solder resist ink to have strong chemical resistance.

[0003] One challenge with black solder resist inks is that black absorbs and blocks light, making it difficult for UV light to penetrate during exposure. This necessitates an efficient initiation system to improve sensitivity. Currently, most black solder resist inks on the market lack good resistance to chemical plating and electroplating. After plating, color changes or decreased adhesion may occur, or the printing thickness may need to be increased to over 20 micrometers. Increasing the thickness raises costs and significantly reduces resolution, making it unsuitable for fine lines.

[0004] Therefore, this application is submitted. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the existing technology and provide an anti-electroplating and chemical-resistant black solder resist ink and its preparation method. The black solder resist ink has excellent anti-electroplating and chemical-resistant effects.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B; Component A comprises the following components in parts by weight: 50-70 parts matrix resin, 4-8 parts photoinitiator, 4-10 parts carbon black, 8-20 parts filler, 8-15 parts solvent, 0.5-2 parts fluorinated leveling agent, 0.5-2 parts defoamer, and 0.5-3 parts dispersant; Component B comprises the following components in parts by weight: 25-40 parts diluent, 20-35 parts phenolic epoxy resin, 8-15 parts triglycidyl isocyanurate, 10-20 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 2-5 parts silane coupling agent, and 15-25 parts solvent; The matrix resin comprises carboxyl-containing phenolic epoxy acrylate, carboxyl-containing bisphenol A epoxy acrylate, and carboxyl-containing acrylic resin in a mass ratio of (25~35):(20~25):(5~10).

[0007] This invention combines the above-mentioned raw materials to obtain a black solder resist ink with excellent electroplating and chemical plating resistance. The black solder resist ink can effectively reduce the printing thickness, enabling even difficult-to-expose black inks to have good exposure effects, good resolution, and broad application prospects.

[0008] This invention employs a matrix resin composed of a specific mass ratio of carboxyl-containing phenolic epoxy acrylate, carboxyl-containing bisphenol A epoxy acrylate, and carboxyl-containing acrylic resin. The carboxyl-containing phenolic epoxy acrylate, carboxyl-containing bisphenol A epoxy acrylate, and carboxyl-containing acrylic resin contain photosensitive groups and alkali-soluble groups, giving the matrix resin excellent photosensitivity and alkali solubility. In the matrix resin, the carboxyl-containing acrylic resin provides basic toughness, preventing paint film cracking. The carboxyl-containing phenolic epoxy acrylate and carboxyl-containing bisphenol A epoxy acrylate serve as a skeleton, forming a three-dimensional network cross-linked structure in the specific system of this invention. This effectively improves the anti-electroplating and chemical plating effects, enabling the development of lines approximately 150μm in diameter, ensuring straight lines without defects or short circuits. Furthermore, after electroplating, the original color is maintained without peeling, swelling, or discoloration, and the coating is evenly distributed along the ink edge.

[0009] The specific B component (curing system) of this invention contains a variety of epoxy resins (all of which are multifunctional epoxy resins), which can react with the carboxyl groups in the matrix resin to increase the crosslinking density. On the other hand, as the carboxyl groups are consumed, the acid resistance and chemical corrosion resistance of the system are improved, thus exhibiting good electroplating resistance and chemical resistance.

[0010] In a preferred embodiment of the present invention, the mass ratio of component A to component B is (2~5):1.

[0011] In a preferred embodiment of the present invention, the acid value of the carboxyl-containing phenolic epoxy acrylate is 40~70 mgKOH / g; The acid value of the carboxyl-containing bisphenol A epoxy acrylate is 45~100 mgKOH / g; The acid value of the carboxyl-containing acrylic resin is 50~100 mgKOH / g.

[0012] In a preferred embodiment of the present invention, the acid value of the carboxyl-containing phenolic epoxy acrylate is 50~65 mgKOH / g; The acid value of the carboxyl-containing bisphenol A epoxy acrylate is 62~98 mgKOH / g; The acid value of the carboxyl-containing acrylic resin is 60~70 mgKOH / g.

[0013] In a preferred embodiment of the present invention, the photoinitiator comprises a first initiator, a second initiator, and bis(2,6-difluoro-3-pyrrolidinyl)dicentaxane in a mass ratio of (3.4~6.5):(0.5~2):(0.1~0.5). The first initiator and the second initiator are different, and each of the first initiator and the second initiator independently comprises at least one of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, and benzophenone.

[0014] The specific photoinitiating system of this invention contains bis(2,6-difluoro-3-pyrrolidinium)titanium. The bis(2,6-difluoro-3-pyrrolidinium)titanium has a wide absorption wavelength range, high activity, and good deep curing ability. When combined with other initiators, it solves the problem of difficult UV curing of black systems.

[0015] As a preferred embodiment of the present invention, the photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, and bis(2,6-difluoro-3-pyrrolidinyldicentaxane) in a mass ratio of (3.4~6.5):(0.5~2):(0.1~0.5).

[0016] In a preferred embodiment of the present invention, the filler includes at least one of talc, barium sulfate, and silica powder.

[0017] As a preferred embodiment of the present invention, the solvent in component A includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isoflurane, N-methylpyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, dodecyl alcohol ester and DBE solvent. The solvent in component B includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isoflurane, N-methylpyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, twelfth alcohol ester, and DBE solvent.

[0018] As a preferred embodiment of the present invention, the reactive diluent includes at least one of trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and pentaerythritol triacrylate; The silane coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0019] In a preferred embodiment of the present invention, the defoamer includes at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate and silicone resin.

[0020] In a preferred embodiment of the present invention, the dispersant includes at least one of polyester dispersants and polyether dispersants.

[0021] As a preferred embodiment of the present invention, the fluorinated leveling agent includes at least one of the leveling agent Efka®-FL 3777 AN and the leveling agent STA-3377.

[0022] In a preferred embodiment of the present invention, the phenolic epoxy resin includes at least one of phenolic epoxy resin NPCN704 and phenolic epoxy resin PNE176. The present invention also provides a method for preparing an anti-electroplating and chemical-resistant black solder resist ink, comprising the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0023] The beneficial effects of the present invention are as follows: the black solder resist ink of the present invention has excellent anti-electroplating and anti-chemical plating effects, the black solder resist ink can effectively reduce the printing thickness, and enable even difficult-to-expose black to have good exposure effect, good resolution, and broad application prospects. Attached Figure Description

[0024] Figure 1 This is a line width diagram of Example 1.

[0025] Figure 2 This is a linewidth diagram of the copper plating thickness in Example 1. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0027] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0028] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0029] In this application, there are no particular restrictions on the specific dispersion and mixing methods.

[0030] Unless otherwise specified, all components, raw materials, or instruments used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0031] The raw material sources for the examples and comparative examples are as follows: Phenolic epoxy acrylate-1 containing carboxyl groups: acid value 60 mg KOH / g, sourced from chemical pharmaceutical company (Wuxi), brand name KR-100.

[0032] Phenolic epoxy acrylate-2 containing carboxyl groups: acid value 50 mg KOH / g, sourced from chemical pharmaceutical company (Wuxi), brand name CCR-4959HW.

[0033] Carboxyl-containing phenolic epoxy acrylate-3: acid value 65 mg KOH / g, sourced from Guangzhou Yingxin, brand name P2103.

[0034] Bisphenol A epoxy acrylate-1 containing carboxyl groups: acid value 98 mgKOH / g, sourced from Nippon Kayaku Co., Ltd., brand name ZAR-1035.

[0035] Bisphenol A epoxy acrylate-2 containing carboxyl groups: acid value 98 mgKOH / g, sourced from Nippon Kayaku Co., Ltd., brand name ZAR-2000.

[0036] Bisphenol A epoxy acrylate-3 containing carboxyl groups: acid value 62 mg KOH / g, sourced from Guangzhou Linchuan Company, brand name LC-880.

[0037] Carboxyl-containing acrylic resin-1: acid value 60mgKOH / g, sourced from Guangzhou Linchuan Company, brand name LC-891.

[0038] Carboxyl-containing acrylic resin-2: acid value 70mgKOH / g, derived from Showa Polymer, brand name BSR-12.

[0039] Poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether: Wengjiang Reagent, brand name PA21391.

[0040] Fluorinated leveling agent-1: Derived from Efka, brand name Efka®-FL 3777 AN.

[0041] Fluorinated leveling agent-2: sourced from Nanxiong Santuo Chemical, brand name leveling agent STA-3377.

[0042] Dispersant: Hypermer KD-1 dispersant.

[0043] Defoamer: Tributyl phosphate.

[0044] Phenolic epoxy resin-1: Sourced from Kunshan Nanya, brand name phenolic epoxy resin NPCN704.

[0045] Phenolic epoxy resin-2: Chang Chun Chemical Co., Ltd., Taiwan Province, brand name PNE176.

[0046] The following embodiments are provided to facilitate understanding of the invention. These embodiments are not intended to limit the scope of the claims.

[0047] Example 1 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0048] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0049] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0050] The matrix resin comprises, by mass ratio 30:22:8, phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0051] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanone in a mass ratio of 4:1:0.2.

[0052] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0053] Example 2 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0054] Component A comprises the following components in parts by weight: 50 parts matrix resin, 8 parts photoinitiator, 4 parts carbon black, 20 parts talc, 8 parts diethylene glycol ethyl ether acetate, 2 parts fluorinated leveling agent-1, 0.5 parts defoamer, and 3 parts dispersant.

[0055] Component B comprises the following components in parts by weight: 25 parts trimethylolpropane triacrylate, 35 parts phenolic epoxy resin-1, 8 parts triglycidyl isocyanurate, 20 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 2 parts γ-mercaptopropyltrimethoxysilane, and 25 parts diethylene glycol ethyl ether acetate.

[0056] The matrix resin comprises carboxyl-containing phenolic epoxy acrylate-1, carboxyl-containing bisphenol A epoxy acrylate-1, and carboxyl-containing acrylic resin-1 in a mass ratio of 25:20:5.

[0057] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthraphenone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanetane in a mass ratio of 6.5:2:0.5.

[0058] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0059] Example 3 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0060] Component A comprises the following components in parts by weight: 70 parts matrix resin, 4 parts photoinitiator, 4 parts carbon black, 20 parts talc, 8 parts diethylene glycol ethyl ether acetate, 2 parts fluorinated leveling agent-1, 0.5 parts defoamer, and 3 parts dispersant.

[0061] Component B comprises the following components in parts by weight: 25 parts trimethylolpropane triacrylate, 35 parts phenolic epoxy resin-1, 8 parts triglycidyl isocyanurate, 20 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 2 parts γ-mercaptopropyltrimethoxysilane, and 25 parts diethylene glycol ethyl ether acetate.

[0062] The matrix resin comprises, by mass ratio of phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0063] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthraphenone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanone in a mass ratio of 3.4:0.5:0.1.

[0064] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0065] Example 4 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0066] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-2, 1.5 parts defoamer, and 2 parts dispersant.

[0067] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-2, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0068] The matrix resin comprises, by mass ratio 30:22:8, phenolic epoxy acrylate-2 containing carboxyl groups, bisphenol A epoxy acrylate-2 containing carboxyl groups, and acrylic resin-2 containing carboxyl groups.

[0069] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanone in a mass ratio of 4:1:0.2.

[0070] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0071] Example 5 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0072] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0073] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0074] The matrix resin comprises carboxyl-containing phenolic epoxy acrylate-3, carboxyl-containing bisphenol A epoxy acrylate-3, and carboxyl-containing acrylic resin-2 in a mass ratio of 30:22:8.

[0075] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanone in a mass ratio of 4:1:0.2.

[0076] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0077] Example 6 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0078] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0079] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0080] The matrix resin comprises, by mass ratio 30:22:8, phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0081] The photoinitiator comprises 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzophenone, and bis(2,6-difluoro-3-pyrrolidinyl)dicenoctanetane in a mass ratio of 4:1:0.2.

[0082] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0083] Example 7 An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0084] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0085] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0086] The matrix resin comprises, by mass ratio 30:22:8, phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0087] The photoinitiator comprises 1-hydroxycyclohexylphenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and bis(2,6-difluoro-3-pyrrolephenyldicyclopentadiene) in a mass ratio of 4:1:0.2.

[0088] The preparation method of the aforementioned anti-electroplating and chemical-resistant black solder resist ink includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

[0089] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the amount of each raw material is different, but everything else is the same.

[0090] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0091] Component A comprises the following components in parts by weight: 40 parts matrix resin, 10 parts photoinitiator, 3 parts carbon black, 22 parts talc, 6 parts diethylene glycol ethyl ether acetate, 2.5 parts fluorinated leveling agent-1, 0.4 parts defoamer, and 4 parts dispersant.

[0092] Component B comprises the following components in parts by weight: 20 parts trimethylolpropane triacrylate, 15 parts phenolic epoxy resin-1, 5 parts triglycidyl isocyanurate, 8 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 6 parts γ-mercaptopropyltrimethoxysilane, and 12 parts diethylene glycol ethyl ether acetate.

[0093] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the amount of each raw material is different, but everything else is the same.

[0094] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0095] Component A comprises the following components in parts by weight: 80 parts matrix resin, 2 parts photoinitiator, 12 parts carbon black, 6 parts talc, 20 parts diethylene glycol ethyl ether acetate, 0.4 parts fluorinated leveling agent-1, 3 parts defoamer, and 0.4 parts dispersant.

[0096] Component B comprises the following components in parts by weight: 45 parts trimethylolpropane triacrylate, 40 parts phenolic epoxy resin-1, 18 parts triglycidyl isocyanurate, 25 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 1 part γ-mercaptopropyltrimethoxysilane, and 28 parts diethylene glycol ethyl ether acetate.

[0097] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the matrix resin is different, but everything else is the same.

[0098] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0099] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0100] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0101] The matrix resin comprises, in a mass ratio of 20:20:20, carboxyl-containing phenolic epoxy acrylate-1, carboxyl-containing bisphenol A epoxy acrylate-1, and carboxyl-containing acrylic resin-1.

[0102] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the matrix resin is different, but everything else is the same.

[0103] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0104] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0105] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0106] The matrix resin comprises, by mass ratio 40:10:10, phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0107] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the matrix resin is different, but everything else is the same.

[0108] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0109] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0110] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0111] The matrix resin comprises phenolic epoxy acrylate-1 containing carboxyl groups and bisphenol A epoxy acrylate-1 containing carboxyl groups in a mass ratio of 30:22.

[0112] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the matrix resin is different, but everything else is the same.

[0113] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0114] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0115] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0116] The matrix resin comprises bisphenol A epoxy acrylate-1 containing carboxyl groups and acrylic resin-1 containing carboxyl groups in a mass ratio of 22:8.

[0117] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that the matrix resin is different, but everything else is the same.

[0118] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0119] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0120] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0121] The matrix resin comprises carboxyl-containing phenolic epoxy acrylate-1 and carboxyl-containing acrylic resin-1 in a mass ratio of 30:8.

[0122] Comparative Example 8 The difference between Comparative Example 8 and Example 1 is that the photoinitiator is different, but everything else is the same.

[0123] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0124] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0125] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 15 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0126] The matrix resin comprises, by mass ratio 30:22:8, phenolic epoxy acrylate-1 containing carboxyl groups, bisphenol A epoxy acrylate-1 containing carboxyl groups, and acrylic resin-1 containing carboxyl groups.

[0127] The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone and 2-isopropylthioxanthraphenone in a mass ratio of 4:1.

[0128] Comparative Example 9 The difference between Comparative Example 9 and Example 1 is that the curing agent is different, but everything else is the same.

[0129] An anti-electroplating and anti-chemical plating black solder resist ink, comprising component A and component B in a mass ratio of 4:1.

[0130] Component A comprises the following components in parts by weight: 60 parts matrix resin, 5.2 parts photoinitiator, 6 parts carbon black, 12 parts talc, 12.1 parts diethylene glycol ethyl ether acetate, 1.2 parts fluorinated leveling agent-1, 1.5 parts defoamer, and 2 parts dispersant.

[0131] Component B comprises the following components in parts by weight: 30 parts trimethylolpropane triacrylate, 25 parts phenolic epoxy resin-1, 10 parts triglycidyl isocyanurate, 3 parts γ-mercaptopropyltrimethoxysilane, and 17 parts diethylene glycol ethyl ether acetate.

[0132] Test case 1. Screen printing Lay out the printing area with transparent tape. Pour the black solder resist ink from the examples and comparative examples onto a 250-mesh screen. Then place the PCB board / aluminum substrate to be printed under the printing area. Gently scrape the ink onto the printing area with a squeegee. Then press down firmly with the squeegee at a 75-degree angle to the screen and scrape across the screen printing area. Ensure even pressure and scrape twice. Control the thickness to 10 micrometers to obtain a printed ink sample for later use.

[0133] 2. Pre-baking, exposure and development, post-curing Place the ink sample in an oven at 80°C for 30 minutes, then attach the developing film and expose it under ultraviolet light for curing. Next, develop the desired pattern in a developing solution with a sodium carbonate concentration of 0.8-1.2%, and finally bake it in an oven at 150°C for 1 hour to complete the production of the ink curing film.

[0134] 1. Resolution: The linewidth was observed and measured using a 500x microscope (the average of three test groups was taken). The linewidth in Example 1 is shown below. Figure 1 As shown, record the distribution of lines (whether there are gaps, broken lines, non-straight lines, or residual / short circuit phenomena).

[0135] A line width of <160μm is defined as acceptable, and a line width of ≥160μm is defined as unacceptable.

[0136] 2. Electroplating resistance: No discoloration, no peeling, no defects, and 5B adhesion after plating (electroplating conditions: 5% sulfuric acid, 50℃, current 0.15A, 30 minutes).

[0137] 3. Chemical resistance: No discoloration, no peeling, no defects, and 5B adhesion after plating (chemical plating conditions: pH=4, 80℃, 30 minutes).

[0138] Among them, such as Figure 2 As shown, the black solder resist ink of Example 1 can still maintain its original color after copper electroplating, without peeling, swelling or discoloration, and the plating layer can be evenly distributed along the edge of the ink.

[0139] Table 1 As can be seen from Table 1, the black solder resist ink described in this invention can effectively reduce printing thickness, enabling even difficult-to-expose black inks to have good exposure effects and good resolution, and has broad application prospects.

[0140] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A black solder resist ink that is resistant to electroplating and chemical plating, characterized in that, Includes component A and component B; Component A comprises the following components in parts by weight: 50-70 parts matrix resin, 4-8 parts photoinitiator, 4-10 parts carbon black, 8-20 parts filler, 8-15 parts solvent, 0.5-2 parts fluorinated leveling agent, 0.5-2 parts defoamer, and 0.5-3 parts dispersant; Component B comprises the following components in parts by weight: 25-40 parts diluent, 20-35 parts phenolic epoxy resin, 8-15 parts triglycidyl isocyanurate, 10-20 parts poly[(2-epoxyethylene)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 2-5 parts silane coupling agent, and 15-25 parts solvent; The matrix resin comprises carboxyl-containing phenolic epoxy acrylate, carboxyl-containing bisphenol A epoxy acrylate, and carboxyl-containing acrylic resin in a mass ratio of (25~35):(20~25):(5~10).

2. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The mass ratio of component A to component B is (2~5):

1.

3. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The acid value of the carboxyl-containing phenolic epoxy acrylate is 40~70 mgKOH / g; The acid value of the carboxyl-containing bisphenol A epoxy acrylate is 45~100 mgKOH / g; The acid value of the carboxyl-containing acrylic resin is 50~100 mgKOH / g.

4. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The acid value of the carboxyl-containing phenolic epoxy acrylate is 50~65 mgKOH / g; The acid value of the carboxyl-containing bisphenol A epoxy acrylate is 62~98 mgKOH / g; The acid value of the carboxyl-containing acrylic resin is 60~70 mgKOH / g.

5. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The photoinitiator comprises a first initiator, a second initiator, and bis(2,6-difluoro-3-pyrrolidinyl)titanium oxide in a mass ratio of (3.4~6.5):(0.5~2):(0.1~0.5). The first initiator and the second initiator are different, and each of the first initiator and the second initiator independently includes at least one of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, and benzophenone.

6. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 5, characterized in that, The photoinitiator comprises 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthraquinone, and bis(2,6-difluoro-3-pyrrolidinyldicenoctanone) in a mass ratio of (3.4~6.5):(0.5~2):(0.1~0.5).

7. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The filler includes at least one of talc, barium sulfate, and silica powder.

8. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The solvent in component A includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isoflurane, N-methylpyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, dodecyl alcohol ester and DBE solvent; The solvent in component B includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isoflurane, N-methylpyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, twelfth alcohol ester, and DBE solvent.

9. The anti-electroplating and anti-chemical plating black solder resist ink according to claim 1, characterized in that, The reactive diluent includes at least one of trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and pentaerythritol triacrylate; The silane coupling agent includes at least one of γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

10. The method for preparing the anti-electroplating and anti-chemical plating black solder resist ink according to any one of claims 1 to 9, characterized in that, Includes the following steps: Mix all raw materials in component A evenly, mix all raw materials in component B evenly, grind components A and B separately to a fineness of less than 5μm, and then mix components A and B evenly to obtain an anti-electroplating and anti-chemical plating black solder resist ink.

Images