阅读说明：本技术 一种感光树脂及其在制备液态感光阻焊油墨中的应用 (Photosensitive resin and application thereof in preparation of liquid photosensitive solder resist ink ) 是由 胡仕锬 沈杰 于 2019-11-11 设计创作，主要内容包括：本发明公开了一种感光树脂及其在制备液态感光阻焊油墨中的应用,所述的感光树脂包含下述重量份的原料：双酚A型环氧丙烯酸树脂200～300份,二乙二醇乙醚醋酸酯180～190份,丙烯酸45～90份,N、N-二甲基苄氨2～8份,对苯二酚2～8份,四氢邻苯二甲酸酐45～90份；本发明中采用上述感光树脂的合成作为主体树脂相比现有技术中的主体树脂具有更好的韧性,更优异的亲水性和生产过程中更优异的脱水性能；将上述感光树脂添加到液态感光阻焊油墨的配方中大大降低油墨的有机挥发物(VOCs)排放量。(The invention discloses a photosensitive resin and an application thereof in preparing liquid photosensitive solder resist ink, wherein the photosensitive resin comprises the following raw materials in parts by weight: 200-300 parts of bisphenol A epoxy acrylic resin, 180-190 parts of diethylene glycol ethyl ether acetate, 45-90 parts of acrylic acid, 2-8 parts of N, N-dimethyl benzylamine, 2-8 parts of hydroquinone and 45-90 parts of tetrahydrophthalic anhydride; compared with the main resin in the prior art, the main resin synthesized by adopting the photosensitive resin has better toughness, more excellent hydrophilicity and more excellent dehydration performance in the production process; the photosensitive resin is added into the formula of the liquid photosensitive solder resist ink, so that the emission of Volatile Organic Compounds (VOCs) of the ink is greatly reduced.)

1. A photosensitive resin characterized by: the resin comprises the following raw materials in parts by weight: 200-300 parts of bisphenol A epoxy acrylic resin, 180-190 parts of diethylene glycol ethyl ether acetate, 45-90 parts of acrylic acid, 2-8 parts of N, N-dimethyl benzylamine, 2-8 parts of hydroquinone and 45-90 parts of tetrahydrophthalic anhydride.

2. A photosensitive resin according to claim 1, wherein: the bisphenol A type epoxy acrylic resin is modified by special epoxy resin.

3. A photosensitive resin according to claim 1 or 2, wherein: the resin comprises the following raw materials in parts by weight: 235 parts of bisphenol A epoxy acrylic resin, 185 parts of diethylene glycol ethyl ether acetate, 72 parts of acrylic acid, N, N-dimethyl benzylamine 4 parts, hydroquinone 4 parts and tetrahydrophthalic anhydride 65 parts.

4. A method for producing a photosensitive resin according to claim 3, characterized in that: the preparation method comprises the following steps: adding 235 g of special epoxy resin modified bisphenol A epoxy acrylic resin and 185 g of diethylene glycol ethyl ether acetate into a three-neck flask, after the dissolution is finished, adding 72 g of acrylic acid, 4 g of N, N-dimethyl benzylamine and 4 g of hydroquinone, heating to 100 ℃, reacting for 10 hours, adding 65 g of tetrahydrophthalic anhydride, heating to 110 ℃, reacting for 5 hours, and obtaining the photosensitive resin with the acid value of 59mgKOH/g and the solid content of 68%.

5. The liquid photosensitive solder resist ink is characterized in that: the ink comprises the following raw materials in parts by weight: 20-24 parts of special epoxy modified photosensitive resin, 5-8 parts of common photosensitive resin, 5-8 parts of acrylic monomer, 0.5-4 parts of UV initiator, 4-8 parts of epoxy resin, 15-30 parts of filler, 0.5-1 part of pigment, 0.5-1 part of flatting agent, 0.5-1 part of defoaming agent, 0.01-0.03 part of stabilizer and 20-30 parts of deionized water.

6. The liquid photosensitive solder resist ink according to claim 5, wherein:

the filler is barium sulfate;

the pigment is phthalocyanine green;

the UV initiator is selected from at least one of alpha-hydroxyketone, alpha-aminoketone, bisacylphosphine oxide, alpha-hydroxyacetone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, ethyl 4-dimethylamino-benzoate, isopropyl thioxanthone, 1-hydroxycyclohexylphenylketone and diphenyl iodonium salt hexafluorophosphate;

the leveling agent is selected from one of fluorocarbon modified polyacrylamide, fluorine modified acrylate and fluorine-polyether modified polysiloxane.

7. The liquid photosensitive solder resist ink according to claim 5 or 6, wherein: the ink comprises the following raw materials in parts by weight: 23.6 parts of special epoxy modified photosensitive resin, 6 parts of common photosensitive resin, 6 parts of acrylic monomer, 2 parts of UV initiator, 5 parts of epoxy resin, 20 parts of filler, 0.7 part of pigment, 0.6 part of flatting agent, 0.6 part of defoaming agent, 0.01 part of stabilizer and 25 parts of deionized water.

8. The liquid photosensitive solder resist ink according to claim 7, wherein: the liquid photosensitive solder resist ink is coated by screen printing or a roller, is pre-baked at 75-95 ℃ to obtain a dry film with the thickness of 20-25um, and is exposed, wherein the UV exposure energy is 200-²The number of exposure grids is 9-12, wherein the exposure rule adopted for exposure is 21 exposure rules, 1% Na₂CO₃Developing with the developing solution for 60 seconds to obtain clear development, and thermally curing at 150 ℃ for 60 minutes to obtain a solder mask; the surface hardness of the coating is 6H, the coating does not crack or separate after being dipped in tin for three times at 288 ℃ for 10 seconds, and the coating does not lose oil or foam after the gold electroplating and gold melting process.

Technical Field

The invention belongs to the technical field of electronic materials and the technical field of high polymer material chemical industry, and particularly relates to photosensitive resin and application thereof in preparation of liquid photosensitive solder resist ink.

Background

With the development of miniaturization, ultra-thinning and light weight of electronic products, the circuit of a circuit board (PCB) is developed towards high concentration, a new technology and a new process are required to be adopted for the production of the circuit board (PCB) to meet the requirements of fine spacing with higher density and smaller geometric dimension, one key material is a layer of high-molecular organic film coated on a substrate to protect the solder resist ink of the circuit board, the solder resist ink cannot crack when the solder is subjected to high temperature, the solder cannot permeate, and the oil cannot be foamed or dropped when the electroless gold plating is carried out.

At present, all the ink used in PCB production is organic solvent type, and the solvent type photosensitive solder resist ink is one of the ink with larger dosage, which causes larger discharge of Volatile Organic Compounds (VOCs) and serious pollution, and increases the production cost of PCB production.

Disclosure of Invention

The invention aims to solve the technical problems that the existing photosensitive solder resist ink is solvent type, the discharge amount of Volatile Organic Compounds (VOCs) is large, the environmental protection and odor problems of the ink are unfavorable for first-line users, the toughness of the prepared organic coating is insufficient, and the high-precision PCB product is difficult to manufacture; aiming at the defects in the prior art, the invention aims to provide a photosensitive resin and an application thereof in preparing liquid photosensitive solder resist ink, wherein the photosensitive resin comprises the following raw materials in parts by weight: 200-300 parts of bisphenol A epoxy acrylic resin, 150-200 parts of diethylene glycol ethyl ether acetate, 45-90 parts of acrylic acid, 2-8 parts of N, N-dimethyl benzylamine, 2-8 parts of hydroquinone and 45-90 parts of tetrahydrophthalic anhydride; compared with the main resin in the prior art, the main resin synthesized by adopting the photosensitive resin has better toughness, more excellent hydrophilicity and more excellent dehydration performance in the production process; the photosensitive resin is added into the formula of the liquid photosensitive solder resist ink, so that the emission of Volatile Organic Compounds (VOCs) of the ink is greatly reduced.

In order to realize the purpose of the invention, the invention adopts the following technical scheme:

the photosensitive resin comprises the following raw materials in parts by weight: 200-300 parts of bisphenol A epoxy acrylic resin, 180-190 parts of diethylene glycol ethyl ether acetate, 45-90 parts of acrylic acid, 2-8 parts of N, N-dimethyl benzylamine, 2-8 parts of hydroquinone and 45-90 parts of tetrahydrophthalic anhydride;

preferably, the bisphenol A type epoxy acrylic resin is a bisphenol A type epoxy acrylic resin modified by special epoxy resin;

preferably, the resin comprises the following raw materials in parts by weight: 235 parts of bisphenol A epoxy acrylic resin, 185 parts of diethylene glycol ethyl ether acetate, 72 parts of acrylic acid, N, N-dimethyl benzylamine 4 parts, hydroquinone 4 parts and tetrahydrophthalic anhydride 65 parts.

A preparation method of photosensitive resin comprises the following steps: adding 235 g of special epoxy resin modified bisphenol A epoxy acrylic resin and 185 g of diethylene glycol ethyl ether acetate into a three-neck flask, after the dissolution is finished, adding 72 g of acrylic acid, 4 g of N, N-dimethyl benzylamine and 4 g of hydroquinone, heating to 100 ℃, reacting for 10 hours, adding 65 g of tetrahydrophthalic anhydride, heating to 110 ℃, reacting for 5 hours, and obtaining the photosensitive resin with the acid value of 59mgKOH/g and the solid content of 68%.

The liquid photosensitive solder resist ink comprises the following raw materials in parts by weight: 20-24 parts of special epoxy modified photosensitive resin, 5-8 parts of common photosensitive resin, 5-8 parts of acrylic monomer, 0.5-4 parts of UV initiator, 4-8 parts of epoxy resin, 15-30 parts of filler, 0.5-1 part of pigment, 0.5-1 part of flatting agent, 0.5-1 part of defoaming agent, 0.01-0.03 part of stabilizer and 20-30 parts of deionized water.

Preferably, the filler is barium sulfate; the pigment is phthalocyanine green; the UV initiator is selected from at least one of alpha-hydroxyketone, alpha-aminoketone, bisacylphosphine oxide, alpha-hydroxyacetone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, ethyl 4-dimethylamino-benzoate, isopropyl thioxanthone, 1-hydroxycyclohexylphenylketone and diphenyl iodonium salt hexafluorophosphate; the flatting agent is selected from one of fluorocarbon modified polyacrylamide, fluorine modified acrylate and fluorine-polyether modified polysiloxane; the defoaming agent is a polymer defoaming agent without organic silicon, and the model is BYK-052.

Preferably, the ink comprises the following raw materials in parts by weight: 23.6 parts of special epoxy modified photosensitive resin, 6 parts of common photosensitive resin, 6 parts of acrylic monomer, 2 parts of UV initiator, 5 parts of epoxy resin, 20 parts of filler, 0.7 part of pigment, 0.6 part of flatting agent, 0.6 part of defoaming agent, 0.01 part of stabilizer and 25 parts of deionized water;

preferably, the liquid photosensitive solder resist ink is coated by screen printing or a roller, is pre-baked at 75-95 ℃ to obtain a dry film with the thickness of 20-25um, and is exposed,UV exposure energy of 200-²The number of exposure grids is 9-12, wherein the exposure rule adopted for exposure is 21 exposure rules, 1% Na₂CO₃Developing with the developing solution for 60 seconds to obtain clear development, and thermally curing at 150 ℃ for 60 minutes to obtain a solder mask; the surface hardness of the coating is 6H, the coating does not crack or separate after being dipped in tin for three times at 288 ℃ for 10 seconds, and the coating does not lose oil or foam after the gold electroplating and gold melting process.

Compared with the main resin in the prior art, the main resin synthesized by adopting the photosensitive resin has better toughness, more excellent hydrophilicity and more excellent dehydration performance in the production process; the photosensitive resin is added into the formula of the liquid photosensitive solder resist ink to greatly reduce the emission of Volatile Organic Compounds (VOCs) of the ink; the ionic water is used as a main liquid carrier, so that the odor and the Volatile Organic Compounds (VOCs) are low, the production cost can be reduced, and the benefit is improved; the novel special epoxy modified photosensitive resin has more excellent physical and chemical properties and can better meet the requirements of clients.

Detailed Description

To facilitate understanding of the present invention, examples are given below which may further supplement and explain the present invention, but the present invention is not limited to these examples.

The preparation of the self-made photosensitive resin of the present invention is first specifically illustrated by examples: