CN112063226B - Photocuring PCB circuit board protective ink - Google Patents

Photocuring PCB circuit board protective ink Download PDF

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CN112063226B
CN112063226B CN202011142653.5A CN202011142653A CN112063226B CN 112063226 B CN112063226 B CN 112063226B CN 202011142653 A CN202011142653 A CN 202011142653A CN 112063226 B CN112063226 B CN 112063226B
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photoinitiator
photoinitiators
bisphenol
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CN112063226A (en
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徐益清
岳利培
刘国强
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Wuxi Bojia Electronic New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses a photocuring PCB circuit board protective ink, and belongs to the technical field of printed circuit boards. The photocuring PCB circuit board protective ink comprises the following components in parts by weight: 25-40 parts of polyethyleneimine modified UV resin, 20-30 parts of carboxylated bisphenol S epoxy acrylate, 15-30 parts of low-viscosity high-functionality polyurethane acrylate, 30-50 parts of hyperbranched structure S-containing polyester acrylate, 1-10 parts of photoinitiator and 0.5-5 parts of auxiliary agent. The photocuring PCB circuit board protective ink prepared by the invention does not contain organic solvent and diluent, is green and environment-friendly, has the advantages of good resolution, high hardness, good alkali etching resistance, good visco-film property and the like, and is suitable for producing high-precision PCB inner layer circuit boards with smaller line width and line distance.

Description

Photocuring PCB circuit board protective ink
Technical Field
The invention belongs to the technical field of printed circuit boards, relates to a light-cured PCB (printed circuit board) protective ink, and particularly relates to a UV (ultraviolet) light-cured PCB protective ink applied to the manufacture of a printed circuit board.
Background
Printed Circuit Boards (PCBs) are important electronic components and generally need to be obtained through processes such as photocuring ink, drying, mask covering, exposure, development, etching, and peeling of a photocuring ink protective layer. The most critical step is how to realize the arrangement of electronic circuits on the copper-clad plate, because the PCB can only play a role when the arrangement of the circuits is realized. At present, the design of an electronic circuit is basically realized by etching on a copper-clad plate, so that the circuit etching is a very critical step, and the effect of the circuit etching is directly related to the quality of a PCB (printed circuit board).
The photocuring printing ink forms an ink layer after being dried, and the ink layer can be subjected to crosslinking curing or degradation reaction to form a protective layer during exposure. During development, the developing solution only dissolves the ink layer, the residual protective layer forms a pattern corresponding to the mask plate, the edge lines of the protective layer are more orderly, the resolution of the photocuring ink is better, and the manufacturing precision of the PCB is higher. General solvent-based ink contains a large amount of organic solvents such as toluene, benzene, butanone, ethyl acetate, butyl acetate and the like, and the volatile solvents pollute the air and harm the health of operators in the using process of the solvent-based ink. The UV light curing technology has the advantages of environmental protection, no VOC emission, low energy consumption, rapid curing and the like, and becomes a new green coating material technology with great development potential in the future. Conventional UV inks do not contain volatile organic solvents, but in order to solve the problem of excessive prepolymer viscosity, a large amount of reactive diluent must be added to dilute the prepolymer in order to provide it with a certain fluidity, whereas currently used diluents are generally acrylate compounds which are irritating and toxic to the users and touch persons of the inks to varying degrees. When the existing light-cured printing ink is exposed, the optical fiber is easy to scatter when passing through the printing ink layer, so that the edge lines of the protective layer are not cured uniformly, and when the printing ink layer is dissolved by adopting a developing solution, the edge lines of the protective layer are not uniform, so that the resolution of the light-cured printing ink is poor, and the manufacturing of a PCB (printed Circuit Board) with high-precision requirements is difficult to meet.
Patent application CN108192415A describes a UV sensitive aqueous PCB circuit protection ink, although water is used as dispersion medium to achieve environmental protection effect, the molecular structure mainly composed of acrylate has lower optical refractive index, and it is difficult to meet the requirement of high precision. CN109868003A and CN109868004A disclose a photo-curable ink mainly containing alkali-soluble UV resin or carboxyl-modified epoxy acrylate, respectively, which has the following problems: although the UV light curing system is adopted, a large amount of diluents and solvents are added for reducing the viscosity of the resin, and the system is not environment-friendly; in order to improve the optical refractive index of the ink, a large amount of inorganic filler is added, so that the dispersion uniformity and the curing efficiency of an ink system are reduced.
Therefore, how to prepare the PCB protection ink which is completely green and environment-friendly, does not contain a diluent and an organic solvent, has high refractive index, high resolution and high precision becomes a great challenge.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the photocuring PCB circuit board protective ink which does not use organic solvents and diluents and is completely green and environment-friendly; meanwhile, the problems of poor resolution of the photocuring ink layer, poor alkali etching resistance, difficulty in meeting the PCB manufacturing requirement on high precision and the like are solved.
Specifically, the invention firstly provides a photocuring PCB circuit board protective ink which comprises the following components in parts by weight:
Figure BDA0002738691400000021
the polyethyleneimine modified UV resin is prepared from polyethyleneimine and glycidyl (meth) acrylate (ether) through polymerization reaction;
the carboxylated bisphenol S epoxy acrylate is obtained by carrying out a ring-opening reaction on a carboxyl acrylate monomer and bisphenol S epoxy resin to obtain epoxy acrylate, and then carrying out a ring-opening reaction on the epoxy acrylate and anhydride; the carboxyl acrylate monomer is prepared by the ring-opening reaction of hydroxyethyl (meth) acrylate and anhydride.
Further, the glycidyl (meth) acrylate (ether) refers to any one or more of glycidyl acrylate, glycidyl methacrylate and glycidyl methacrylate ether.
Further, the hydroxyethyl (meth) acrylate refers to any one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
Further, in a possible implementation manner, the normal-temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800-1500 mpa.s (25 ℃), the acid value is 60-90 mgKOH/g, the functionality is 9-15, and the molar mass is 1000-2000 g/mol.
Further, in a possible implementation manner, the normal temperature viscosity of the S-containing polyester acrylate with the hyperbranched structure is 500-800 mpa.s (25 ℃), the acid value is 2-10 mgKOH/g, the functionality is 6-12, the molar mass is 6000-10000 g/mol, and the refractive index is 1.61-1.7.
Further, in a possible implementation manner, the polyethyleneimine has a molar mass of 100-300 g/mol and an acid value of 40-150 mgKOH/g.
Further, in a possible implementation manner, the molar mass of the carboxylated bisphenol S epoxy acrylate is 2000-6000 g/mol, the acid value is 40-100 mgKOH/g, and the refractive index is 1.61-1.7.
Further, in a possible implementation manner, the epoxy equivalent (namely, the value of the average molecular weight of the epoxy resin divided by the number of epoxy groups contained in each molecule) of the bisphenol S epoxy resin is 160-350 g/mol, and the softening point is 60-180 ℃.
Further, in a possible implementation manner, the acid anhydride is selected from at least one of maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, methyl hexahydrophthalic anhydride and succinic anhydride.
Further, in a possible implementation manner, the photoinitiator is selected from at least one of acylphosphine oxide photoinitiators, acetophenone photoinitiators, thioxanthone photoinitiators, benzophenone photoinitiators, aminophenylketone photoinitiators, tertiary amine photoinitiators, benzoin photoinitiators, anthraquinone photoinitiators, diphenyltitanocene photoinitiators, acridine photoinitiators and triarylimidazole dimer photoinitiators.
Further, the benzoin photoinitiator may be at least one of benzoin photoinitiators such as benzoin, benzoin methyl ether, benzoin dimethyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin n-butyl ether, benzoin alkyl ether and the like; the acetophenone photoinitiator can be at least one of acetophenone photoinitiators such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone and 1, 1-dichloroacetophenone; the amino acetophenone photoinitiator can be at least one of amino acetophenone photoinitiators such as 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, N-dimethylamino acetophenone and the like; the acylphosphine oxide photoinitiator may be at least one of acylphosphine oxide photoinitiators such as 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl phenylphosphonate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, acylphosphine oxide, diethyltrimethylbenzoyl phosphate, trimethylbenzoyl diphenylphosphine oxide, and bisbenzoylphenylphosphine oxide; the benzophenone photoinitiator can be at least one of benzophenone, 4-methylbenzophenone, 4-bis (diethylamino) benzophenone (michelson), 4-bis (dimethylamino) benzophenone and other benzophenone photoinitiators; the anthraquinone photoinitiator can be at least one of anthraquinone photoinitiators such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; the thioxanthone photoinitiator may be at least one of thioxanthone photoinitiators such as 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2-isopropylthioxanthone; the triaryl imidazole dimer photoinitiator may be at least one of triaryl imidazole dimer photoinitiators such as 2, 2, 4, 4-tetrakis (2-chlorophenyl) -5, 5-bis (3, 4-dimethoxyphenyl) diimidazole and 2, 2, 5-tris (2-chlorophenyl) -4- (3, 4-dimethylphenyl-4, 5-diphenyldiimidazole, the acridine photoinitiator may be at least one of acridine photoinitiators such as 9-phenylacridine and 1, 7-bis (9-acridinyl) heptane, the diphenyltitanocene photoinitiator may be at least one of diphenyltitanocene photoinitiators such as fluorinated diphenyltitanocene and bis (pentafluorophenyl) titanocene, and the tertiary amine photoinitiator may be triethylamine, At least one of tertiary amine photoinitiator such as triethanolamine and camphorquinone.
Further, in a possible implementation manner, the auxiliary agent is selected from at least one of a stabilizer, a leveling agent, an antifoaming agent, an anti-shrinkage agent, an adhesion promoter, a surface slipping agent, an anti-sagging agent and a polymerization inhibitor.
Further, the stabilizer can be N', N-diphenyl-p-phenylenediamine, the leveling agent can be a BYK-330 leveling agent, the defoaming agent can be BYK-333, the anti-shrinkage agent can be BYK-345, the adhesion promoter can be conventional phosphate ester, the surface slipping agent can be RS-72A, the anti-sagging agent can be BYK-336, and the polymerization inhibitor can be p-hydroxyanisole.
The invention further provides application of the photocuring PCB circuit board protective ink in the field of preparation of printed circuit boards.
Finally, the invention provides a method for preparing a printed circuit board, which utilizes the photocuring PCB circuit board protective ink as the PCB circuit board protective ink.
The invention has the following beneficial effects:
the PCB protection ink does not use organic solvent and diluent, is completely green and environment-friendly, and simultaneously adopts low-viscosity high-functionality polyurethane acrylate and hyperbranched structure S-containing polyester acrylate with lower viscosity to reduce the viscosity of the ink and give consideration to both environment protection and construction operability in order to ensure the low-viscosity index required by ink construction. According to the invention, the high-polarity polyethyleneimine modified UV resin and the carboxylated bisphenol S epoxy acrylate are adopted to ensure the hardness of the ink layer and the alkali solubility required by later etching. And the preparation requirements of the ink layer on high resolution and high precision are ensured by adopting the carboxylated bisphenol S epoxy acrylate containing S heteroatom and the polyester acrylate containing S in hyperbranched structure. Through the mutual matching of the components, when an ink layer of the photo-curing ink is exposed, the photoinitiator initiates a resin system to polymerize, a protective layer with high density is formed, and the alkaline etching resistance is good. The light-cured printing ink is suitable for preparing PCB inner layer circuit boards, and is particularly suitable for producing high-precision PCB inner layer circuit boards with small line width and line distance.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to embodiments, and the description in this section is only exemplary and explanatory, and should not be construed as limiting the scope of the present invention in any way.
The resolution of the photo-curable ink can be evaluated by the dissolution rate of the ink layer in the developer, and after exposure, the ink layer undergoes crosslinking curing or other reactions to form a protective layer that is not easily dissolved in a weak alkaline protective solution, while the ink layer where no exposure occurs is easily dissolved in a weak alkaline solution. The regularity of the lines at the edges of the protective layer is represented by the dissolution rate of the ink layer in the developing solution. The slow development speed (slow dissolution speed of the ink layer) can cause that part of the ink layer is not completely dissolved and remains on the edge of the pattern, thereby causing poor resolution and even failing to resolve the pattern. The development speed is high (the dissolution speed of the ink layer is high), so that the edge of the protective layer is attacked by alkali solution, the edge of the pattern is irregular, and burrs are formed. Therefore, the developing speed is proper, and the resolution of the photo-curing ink can be improved.
And (3) testing the resolution: first, the photo-curable inks prepared in examples were respectively printed on 12 PCB substrate provided with copper metal layers using a screen printing method (100T polyester screen, 75 degree hardness squeegee). And then, placing the PCB substrate coated with the light-cured printing ink into an oven at 90 ℃ for treating for 10 minutes, and drying the surface to obtain an ink layer with the thickness of about 15 microns. Covering the ink layer with a mask plate, and then adopting 100mj/cm2Exposing the ink layer by using ultraviolet light, and then using NaCO with the mass concentration of 1%3The aqueous solution of (A) at 30 ℃ under a pressure of 1.8kg/m2The development was carried out under the conditions of (1) for a development time of 60s, and a pattern corresponding to the mask was obtained. After development, the line analysis was observed to evaluate the resolution. Evaluation criteria of resolution: the analytic line width is preferably less than 60 micrometers; the circuit width of 60-80 microns can be analyzed to be good; the width of the analytical line is 80-100 microns; the line width can be analyzed as a difference of 100 μm or more.
Murphine test: covering 12 film sheets (mask plates) on one surface of 12 PCB base materials coated with the ink layer, and detecting the contact condition between the film sheets and the ink layer. Evaluation criteria: no film prints are excellent; good with film print but not sticking film; murphine is poor.
And (3) hardness testing: the pencil hardness test was carried out according to the method provided in the Standard GB-T9286-1998 test for marking test of paint and varnish films. Evaluation criteria: the hardness is higher than HB; the hardness is HB-B and good; less than B is a difference.
Alkali etching resistance test: after exposure and development are carried out on 12 PCB base materials, only a protective layer is left on the PCB base materials, then the 12 PCB base materials are put into 50 ℃ alkaline etching solution for etching, and the alkaline etching resistance is evaluated according to the etching attack time of the protective layer to the alkaline etching solution. Evaluation criteria: the alkali etching resistance is excellent when the time is more than 20 minutes; the alkali-resistant etching time is between 10 and 20 minutes; alkali etch resistance times of less than 10 minutes are poor.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
In a first aspect, the invention provides a photocuring PCB circuit board protective ink which comprises the following components in parts by weight:
Figure BDA0002738691400000061
wherein the polyethyleneimine-modified UV resin is prepared from polyethyleneimine and glycidyl (meth) acrylate (ether);
the carboxylated bisphenol S epoxy acrylate is obtained by carrying out a ring-opening reaction on a carboxyl acrylate monomer and bisphenol S epoxy resin to obtain epoxy acrylate, and then carrying out a ring-opening reaction on the epoxy acrylate and anhydride; the carboxyl acrylate monomer is prepared by the ring-opening reaction of hydroxyethyl (meth) acrylate and anhydride.
In the photo-curing ink provided by the embodiment of the invention, the polyethyleneimine modified UV resin contains a certain amount of primary amine groups and secondary amine groups, has good adhesion and good alkali solubility, and contains a large amount of double bonds to participate in UV crosslinking, so that the alkali solubility of the ink is ensured, and the hardness and the alkali etching resistance of the ink are improved. The carboxylated bisphenol S epoxy acrylate contains carboxyl polar groups, so that the alkali solubility of the ink is ensured, the double bonds participate in UV cross-linking curing, the hardness and alkali etching resistance of the ink layer are ensured, and meanwhile, the S heteroatom groups in the molecular chain enable the ink layer to have higher light refractive index, so that the high resolution and high precision of the ink layer are ensured. The low-viscosity high-functionality polyurethane acrylate effectively reduces the viscosity of the printing ink, facilitates construction, ensures that the printing ink layer has higher crosslinking density due to high functionality, and improves the hardness and the alkali etching resistance of the printing ink layer. The hyperbranched structure S-containing polyester acrylate has lower viscosity, effectively reduces the viscosity of the ink, facilitates construction, and ensures higher light refractive index of the ink layer and high resolution and high precision of the ink layer due to the S heteroatom groups in the molecular chain.
In the photo-curable ink provided in this embodiment, the ratio of each component can be arbitrarily adjusted within a defined range.
In the following examples, those whose operations are not subject to the conditions indicated, were performed according to the conventional conditions or the conditions suggested by the manufacturer. The raw materials are conventional products which are commercially available and can be obtained by manufacturers and specifications. Wherein the leveling agent is a conventional BYK-330 leveling agent of BYK company, the anti-sagging agent is BYK-336 of BYK company, the surface slipping agent is RS-72A of Japan DIC company, the anti-shrinkage agent is BYK-345 of BYK company, and the defoaming agent is BYK-333 of BYK company; the polymerization inhibitor is p-hydroxyanisole.
Example 1
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 25 parts of polyethyleneimine modified UV resin, 20 parts of carboxylated bisphenol S epoxy acrylate, 15 parts of low-viscosity high-functionality polyurethane acrylate, 30 parts of hyperbranched structure S-containing polyester acrylate, 10 parts of benzophenone such as photoinitiator 4, 4-bis (dimethylamino) benzophenone, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent and 1 part of polymerization inhibitor.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl methacrylate, the molar mass is 100g/mol, and the acid value is 40 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 70 percent of bisphenol S epoxy resin with 20 percent of carboxyl acrylate monomer and then carrying out ring-opening acidification with 10 percent of methyl hexahydrophthalic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 2000g/mol, the acid value is 40mgKOH/g, and the refractive index is 1.61. Wherein the carboxyl acrylate monomer is prepared from 60% methyl hexahydrophthalic anhydride and 40% hydroxyethyl acrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800mpa.s (25 ℃), the acid value is 60mgKOH/g, the functionality is 9, and the molar mass is 1000 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 500mpa.s (25 ℃), the acid value of 2mgKOH/g, the functionality of 6, the molar mass of 6000g/mol and the refractive index of 1.61.
Comparative example 1
This comparative example provides a photocurable ink which differs from the photocurable ink provided in example 1 in that: the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are not added. The contents are as follows: 25 parts of polyethyleneimine modified UV resin, 15 parts of low-viscosity high-functionality polyurethane acrylate, 10 parts of benzophenone such as photoinitiator 4, 4-bis (dimethylamino) benzophenone, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent and 1 part of polymerization inhibitor.
Comparative example 2
This comparative example provides a photocurable ink which differs from the photocurable ink provided in example 1 in that: no carboxylated bisphenol S epoxy acrylate was added. The contents are as follows: 25 parts of polyethyleneimine modified UV resin, 15 parts of low-viscosity high-functionality polyurethane acrylate, 30 parts of hyperbranched structure S-containing polyester acrylate, 10 parts of benzophenone such as photoinitiator 4, 4-bis (dimethylamino) benzophenone, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent and 1 part of polymerization inhibitor.
Comparative example 3
This comparative example provides a photocurable ink which differs from the photocurable ink provided in example 1 in that: the hyperbranched structure of the S-containing polyester acrylate is not added. The contents are as follows: 25 parts of polyethyleneimine modified UV resin, 20 parts of carboxylated bisphenol S epoxy acrylate, 15 parts of low-viscosity high-functionality polyurethane acrylate, 10 parts of benzophenone such as photoinitiator 4, 4-bis (dimethylamino) benzophenone, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent and 1 part of polymerization inhibitor.
Example 2
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 40 parts of polyethyleneimine modified UV resin, 30 parts of carboxylated bisphenol S epoxy acrylate, 30 parts of low-viscosity high-functionality polyurethane acrylate, 50 parts of hyperbranched structure S-containing polyester acrylate, 1 part of photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone, 0.1 part of leveling agent, 0.1 part of defoaming agent, 0.1 part of anti-sagging agent, 0.1 part of polymerization inhibitor and 0.1 part of anti-shrinkage agent.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl methacrylate, and has a molar mass of 300g/mol and an acid value of 150 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 65% of bisphenol S epoxy resin with 20% of carboxyl acrylate monomer and then carrying out ring-opening acidification on the obtained product with 15% of tetrahydrophthalic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 6000g/mol, the acid value is 100mgKOH/g, and the refractive index is 1.7. Wherein the carboxyl acrylate monomer is prepared from 70% tetrahydrophthalic anhydride and 30% hydroxyethyl methacrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 1500mpa.s (25 ℃), the acid value is 90mgKOH/g, the functionality is 15, and the molar mass is 2000 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 800mpa.s (25 ℃), the acid value of 10mgKOH/g, the functionality of 12, the molar mass of 10000g/mol and the refractive index of 1.7.
Example 3
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 30 parts of polyethyleneimine modified UV resin, 23 parts of carboxylated bisphenol S epoxy acrylate, 20 parts of low-viscosity high-functionality polyurethane acrylate, 35 parts of hyperbranched structure S-containing polyester acrylate, 4 parts of photoinitiator 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.5 part of leveling agent, 0.5 part of defoaming agent, 0.5 part of anti-sagging agent, 0.5 part of polymerization inhibitor and 1 part of anti-shrinkage agent.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl acrylate, and has a molar mass of 200g/mol and an acid value of 110 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 65% of bisphenol S epoxy resin with 20% of carboxyl acrylate monomer and then carrying out ring-opening acidification on the obtained product with 15% of tetrahydrophthalic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 4000g/mol, the acid value is 80mgKOH/g, and the refractive index is 1.64. Wherein the carboxyl acrylate monomer is prepared from 70% maleic anhydride and 30% hydroxypropyl methacrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800mpa.s (25 ℃), the acid value is 75mgKOH/g, the functionality is 12, and the molar mass is 1500 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 600mpa.s (25 ℃), the acid value of 6mgKOH/g, the functionality of 8, the molar mass of 8000g/mol and the refractive index of 1.67.
Example 4
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 30 parts of polyethyleneimine modified UV resin, 25 parts of carboxylated bisphenol S epoxy acrylate, 20 parts of low-viscosity high-functionality polyurethane acrylate, 40 parts of hyperbranched structure S-containing polyester acrylate, 5 parts of photoinitiator 2-tert-butyl anthraquinone, 0.5 part of leveling agent, 0.5 part of defoaming agent, 1 part of anti-sagging agent, 0.5 part of polymerization inhibitor and 1 part of anti-shrinkage agent.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl methacrylate, and has a molar mass of 300g/mol and an acid value of 150 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 65% of bisphenol S epoxy resin with 20% of carboxyl acrylate monomer and then carrying out ring-opening acidification with 15% of maleic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 5000g/mol, the acid value is 85mgKOH/g, and the refractive index is 1.66. Wherein the carboxyl acrylate monomer is prepared from 70% maleic anhydride and 30% hydroxypropyl acrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800mpa.s (25 ℃), the acid value is 75mgKOH/g, the functionality is 12, and the molar mass is 1500 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 600mpa.s (25 ℃), the acid value of 5mgKOH/g, the functionality of 10, the molar mass of 9000g/mol and the refractive index of 1.68.
Example 5
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 30 parts of polyethyleneimine modified UV resin, 20 parts of carboxylated bisphenol S epoxy acrylate, 20 parts of low-viscosity high-functionality polyurethane acrylate, 50 parts of hyperbranched structure S-containing polyester acrylate, 8 parts of photoinitiator 2-methyl thioxanthone, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent, 0.5 part of polymerization inhibitor and 1 part of anti-shrinkage agent.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl methacrylate, and has a molar mass of 200g/mol and an acid value of 100 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 65% of bisphenol S epoxy resin with 20% of carboxyl acrylate monomer and then carrying out ring-opening acidification with 15% of maleic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 5000g/mol, the acid value is 85mgKOH/g, and the refractive index is 1.66. Wherein the carboxyl acrylate monomer is prepared from 70% maleic anhydride and 30% hydroxypropyl acrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800mpa.s (25 ℃), the acid value is 75mgKOH/g, the functionality is 12, and the molar mass is 1500 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 600mpa.s (25 ℃), the acid value of 5mgKOH/g, the functionality of 10, the molar mass of 9000g/mol and the refractive index of 1.68.
Example 6
The embodiment provides a photo-curing ink, which comprises the following components in parts by weight: 30 parts of polyethyleneimine modified UV resin, 30 parts of carboxylated bisphenol S epoxy acrylate, 20 parts of low-viscosity high-functionality polyurethane acrylate, 30 parts of hyperbranched structure S-containing polyester acrylate, 8 parts of photoinitiator fluorinated diphenyl titanocene, 1 part of leveling agent, 1 part of defoaming agent, 1 part of anti-sagging agent, 0.5 part of polymerization inhibitor and 1 part of anti-shrinkage agent.
Wherein the polyethyleneimine modified UV resin is formed by polymerization of 80% of polyethyleneimine and 20% of glycidyl methacrylate, and has a molar mass of 200g/mol and an acid value of 100 mgKOH/g. The carboxylated bisphenol S epoxy acrylate is prepared by reacting 65% of bisphenol S epoxy resin with 20% of carboxyl acrylate monomer and then carrying out ring-opening acidification with 15% of maleic anhydride. The molar mass of the carboxylated bisphenol S epoxy acrylate is 5000g/mol, the acid value is 85mgKOH/g, and the refractive index is 1.66. Wherein the carboxyl acrylate monomer is prepared from 70% maleic anhydride and 30% hydroxypropyl acrylate.
Wherein the normal temperature viscosity of the low-viscosity high-functionality polyurethane acrylate is 800mpa.s (25 ℃), the acid value is 75mgKOH/g, the functionality is 12, and the molar mass is 1500 g/mol. The hyperbranched structure S-containing polyester acrylate has the normal temperature viscosity of 600mpa.s (25 ℃), the acid value of 5mgKOH/g, the functionality of 10, the molar mass of 9000g/mol and the refractive index of 1.68.
The photo-curable inks prepared in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1.
TABLE 1 Performance test results of photo-curable inks prepared in examples 1 to 6 and comparative examples 1 to 3
Figure BDA0002738691400000101
The results in the table show that comparative example 1 does not add carboxylated bisphenol S epoxy acrylate and hyperbranched structure S-containing polyester acrylate, and although the cross-linking density of the ink layer is improved by the low-viscosity high-functionality urethane acrylate, the ink layer has excellent visco-film property and good hardness, the optical refractive index of the ink layer is less than 1.6, and the optical resolution and the etching solution resistance of the ink layer are poor, so that the ink layer is not suitable for preparing a high-precision PCB circuit board. Compared with the prior art, the hyperbranched structure S-containing polyester acrylate is added in the comparative example 2, so that the hardness of the ink layer is improved due to high functionality and high crosslinking density, the light refractive index of the ink layer is improved due to the existence of S hetero atoms, and the light resolution and the etching solution resistance of the ink layer are improved to some extent, so that the ink layer is good. Compared with the prior art, the carboxylated bisphenol S epoxy acrylate is added in the comparative example 3, the rigidity of the molecular structure of the bisphenol S resin is stronger, the bisphenol S resin participates in the UV crosslinking reaction, the hardness of the ink layer is excellent, meanwhile, the optical refractive index of the ink layer is improved due to the existence of S hetero atoms, the optical resolution and the etching solution resistance of the ink layer are improved to some extent, and the good performance is achieved.
When the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are added to the ink layer at the same time (examples 1 to 6), both the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are at the lowest content (example 1), both the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are at the highest content (example 2), both the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are at the highest content and at the lowest content (examples 5 and 6), or both the carboxylated bisphenol S epoxy acrylate and the hyperbranched structure S-containing polyester acrylate are added at different proportions (examples 3 and 4), the ink layer has excellent anti-resolution and anti-etching properties while ensuring excellent mucophilin properties and hardness. Therefore, the photocuring PCB circuit board protective ink has higher industrial application value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. The photocuring PCB circuit board protective ink is characterized by comprising the following components in parts by weight:
25-40 parts of polyethyleneimine modified UV resin
20-30 parts of carboxylated bisphenol S epoxy acrylate
15-30 parts of low-viscosity high-functionality polyurethane acrylate
30-50 parts of polyester acrylate with hyperbranched structure and containing S
1-10 parts of photoinitiator
0.5-5 parts of assistant
The polyethyleneimine modified UV resin is prepared from polyethyleneimine and glycidyl (meth) acrylate or glycidyl (meth) acrylate through polymerization reaction;
the carboxylated bisphenol S epoxy acrylate is obtained by carrying out a ring-opening reaction on a carboxyl acrylate monomer and bisphenol S epoxy resin to obtain epoxy acrylate, and then carrying out a ring-opening reaction on the epoxy acrylate and anhydride; the carboxyl acrylate monomer is prepared by performing ring-opening reaction on hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate and anhydride;
the low-viscosity high-functionality polyurethane acrylate has the normal-temperature viscosity of 800-1500 mpa.s, the acid value of 60-90 mgKOH/g, the functionality of 9-15 and the molar mass of 1000-2000 g/mol; the polyester acrylate with the hyperbranched structure containing S has the normal temperature viscosity of 500-800 mpa.s (25 ℃), the acid value of 2-10 mgKOH/g, the functionality of 6-12, the molar mass of 6000-10000 g/mol and the refractive index of 1.61-1.7.
2. The photocuring PCB circuit board protective ink as claimed in claim 1, wherein the polyethyleneimine has a molar mass of 100-300 g/mol and an acid value of 40-150 mgKOH/g; the molar mass of the carboxylated bisphenol S epoxy acrylate is 2000-6000 g/mol, the acid value is 40-100 mgKOH/g, and the refractive index is 1.61-1.7; the epoxy equivalent of the bisphenol S epoxy resin is 160-350 g/mol, and the softening point is 60-180 ℃.
3. The light-curable PCB board protective ink according to claim 1 or 2, wherein the acid anhydride is selected from at least one of maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, methyl hexahydrophthalic anhydride and succinic anhydride.
4. The photocurable PCB wiring board protective ink according to claim 1, wherein the photoinitiator is at least one selected from acylphosphine oxide photoinitiators, acetophenone photoinitiators, thioxanthone photoinitiators, benzophenone photoinitiators, aminoacetone photoinitiators, tertiary amine photoinitiators, benzoin photoinitiators, anthraquinone photoinitiators, diphenyltitanocene photoinitiators, acridine photoinitiators, triarylimidazole dimer photoinitiators.
5. The photocuring PCB wiring board protective ink as defined in claim 4, wherein the benzoin photoinitiator is at least one of benzoin, benzoin methyl ether, benzoin dimethyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin n-butyl ether and benzoin alkyl ether; the acetophenone photoinitiator is at least one of acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone and 1, 1-dichloroacetophenone; the amino acetophenone photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and N, N-dimethylamino acetophenone; the acylphosphine oxide photoinitiator is at least one of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl phenylphosphonate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, acylphosphine oxide, diethyl trimethylbenzoyl phosphate, trimethylbenzoyl diphenylphosphine oxide and bisbenzoyl phenylphosphine oxide; the benzophenone photoinitiator is at least one of benzophenone, 4-methylbenzophenone, 4-bis (diethylamino) benzophenone (michaelis ketone) and 4, 4-bis (dimethylamino) benzophenone; the anthraquinone photoinitiator is at least one of 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; the thioxanthone photoinitiator is at least one of 2-chlorothioxanthone, 2-methyl thioxanthone, 2, 4-dimethyl thioxanthone, 2, 4-diethyl thioxanthone and 2-isopropyl thioxanthone; the triaryl imidazole dimer photoinitiator is at least one of 2, 2, 4, 4-tetra (2-chlorophenyl) -5, 5-bis (3, 4-dimethoxyphenyl) diimidazole and 2, 2, 5-tris (2-chlorophenyl) -4- (3, 4-dimethylphenyl-4, 5-diphenyl diimidazole, the acridine photoinitiator is at least one of 9-phenylacridine and 1, 7-bis (9-acridinyl) heptane, the diphenyl titanocene photoinitiator is at least one of fluorinated diphenyl titanocene and bis (pentafluorophenyl) titanocene, and the tertiary amine photoinitiator is at least one of triethylamine, triethanolamine and camphorquinone.
6. The photocuring PCB wiring board protection ink as claimed in claim 1, wherein the auxiliary agent is at least one selected from a stabilizer, a leveling agent, an antifoaming agent, an anti-cratering agent, an adhesion promoter, a surface slipping agent, an anti-sagging agent and a polymerization inhibitor.
7. The light-cured PCB wiring board protective ink as claimed in claim 1, wherein the light-cured PCB wiring board protective ink is used in the field of preparing printed circuit boards.
8. The use of the photocurable PCB circuit board protective ink as recited in any one of claims 1 to 7 in the field of printed circuit boards.
9. A method for preparing a printed circuit board, characterized in that the method uses the photocurable PCB wiring board protective ink according to any one of claims 1 to 7 as a PCB wiring board protective ink.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496522A (en) * 2016-10-10 2017-03-15 中科院广州化学有限公司南雄材料生产基地 A kind of alkali solubility light-cured epoxy acrylate and preparation method and its etching resisting ink
CN107325642A (en) * 2017-08-24 2017-11-07 广州亦盛环保科技有限公司 A kind of UV ink-jet printing inks, preparation method and the usage
CN109868004A (en) * 2017-12-05 2019-06-11 上海飞凯光电材料股份有限公司 A kind of light-curable ink and pcb board

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496522A (en) * 2016-10-10 2017-03-15 中科院广州化学有限公司南雄材料生产基地 A kind of alkali solubility light-cured epoxy acrylate and preparation method and its etching resisting ink
CN107325642A (en) * 2017-08-24 2017-11-07 广州亦盛环保科技有限公司 A kind of UV ink-jet printing inks, preparation method and the usage
CN109868004A (en) * 2017-12-05 2019-06-11 上海飞凯光电材料股份有限公司 A kind of light-curable ink and pcb board

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