阅读说明：本技术 一种感光阻焊白油及其制备方法 (Photosensitive solder resist white oil and preparation method thereof ) 是由 杨毅 于 2019-11-21 设计创作，主要内容包括：本发明公开了一种感光阻焊白油及其制备方法。该感光阻焊白油包括主剂和固化剂,所述主剂包括：顺酐改性不饱和聚酯、光引发剂、填充剂、流平剂、消泡剂、二价酸酯、气相二氧化硅、稀释剂A；所述固化剂包括：酚醛环氧树脂、双季戊四醇五六丙烯酸酯、羟烷基酰胺、三聚氰胺、钛白粉、二价酸酯、稀释剂B。本发明将含有顺酐改性不饱和聚酯的主剂和固化剂混合后涂覆于印制线路板的基材上,曝光时,油墨层中的光引发剂引发预聚物发生聚合反应得到聚合物,酚醛环氧树脂与聚合物、填料以及其他成分的复配作用下,形成附着力好、硬度好的保护层,而且该阻焊油墨还具有优异的阻焊性能、光泽度高、耐高温及固化时间短的优势。(The invention discloses photosensitive solder resist white oil and a preparation method thereof. The photosensitive solder resist white oil comprises a main agent and a curing agent, wherein the main agent comprises: maleic anhydride modified unsaturated polyester, photoinitiator, filler, flatting agent, defoaming agent, dibasic ester, fumed silica and diluent A; the curing agent comprises: phenolic epoxy resin, dipentaerythritol penta-hexaacrylate, hydroxyalkyl amide, melamine, titanium dioxide, dibasic ester and a diluent B. According to the invention, the main agent containing maleic anhydride modified unsaturated polyester and the curing agent are mixed and coated on the base material of the printed circuit board, when the printed circuit board is exposed, the photoinitiator in the ink layer initiates the prepolymer to perform polymerization reaction to obtain a polymer, and the novolac epoxy resin, the polymer, the filler and other components are compounded to form a protective layer with good adhesion and good hardness.)

1. The photosensitive solder resist white oil is characterized by comprising a main agent and a curing agent, wherein the main agent comprises the following components in parts by weight: 40.0-60.0 parts of maleic anhydride modified unsaturated polyester, 5.0-10.0 parts of photoinitiator, 15.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.2 parts of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-3.0 parts of fumed silica and 10.0 parts of diluent A0; the curing agent comprises the following components in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-9.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-4.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 4.0-8.0 parts of titanium dioxide, 2.0-4.0 parts of dibasic ester and 10.0 parts of diluent B0.

2. The photosensitive solder resist white oil of claim 1, wherein the maleic anhydride modified unsaturated polyester is prepared from the following raw materials in parts by weight: 20-25 parts of maleic anhydride, 10-15 parts of styrene, 20-25 parts of glycidyl ether, 10-13 parts of dibasic ester, 0.5-1.5 parts of initiator, 0.1-0.3 part of catalyst, 0.2-0.4 part of polymerization inhibitor, 10-15 parts of monomer, 0.1-0.15 part of anti-aging agent, 8-12 parts of ethanol and 10-15 parts of hexahydrophthalic anhydride.

3. The photosensitive solder mask white oil of claim 1, wherein the photoinitiator is selected from any one or more of a photoinitiator ITX, a photoinitiator TPO and a photoinitiator 819.

4. The photosensitive solder mask white oil of claim 1, wherein the filler is selected from one or more of barium sulfate, titanium dioxide, talcum powder, kaolin, calcium carbonate, bentonite and carbon black.

5. The photosensitive solder mask white oil of claim 1, wherein the defoaming agent is selected from any one or more of defoaming agent KS-66, defoaming agent KS-603, defoaming agent KS-604 and defoaming agent KS-53.

6. The photosensitive solder mask white oil of claim 1, wherein the diluent A is selected from any one of a non-reactive diluent and a reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of glycerin epoxy resin and propylene oxide butyl ether.

7. The photosensitive solder resist white oil of claim 1, wherein the main agent comprises the following components in parts by weight: 40.0-50.0 parts of maleic anhydride modified unsaturated polyester, 5.0-6.0 parts of photoinitiator, 23.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.0 part of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-1.2 parts of fumed silica and 0-10 parts of diluent A.

8. The photosensitive solder mask white oil of claim 1, wherein the diluent B is selected from any one of a non-reactive diluent and a reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of glycerin epoxy resin and propylene oxide butyl ether.

9. The photosensitive solder resist white oil of claim 1, wherein the curing agent comprises, in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-8.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-3.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 5.0-8.0 parts of titanium dioxide, 2.0-3.0 parts of dibasic ester and 10.0 parts of diluent B0.

10. The preparation method of the photosensitive solder resist white oil as claimed in any one of claims 1 to 9, characterized by comprising the following steps:

(1) uniformly mixing maleic anhydride modified unsaturated polyester, a photoinitiator, a filling agent, a flatting agent, a defoaming agent, dibasic acid ester and fumed silica, grinding for 1-5 times, adding a diluent A, uniformly mixing, filtering and canning to obtain a main agent;

(2) uniformly mixing novolac epoxy resin, dipentaerythritol penta-hexaacrylate, hydroxyalkylamide, melamine, titanium dioxide and dibasic acid ester, grinding for 1-5 times, adding diluent B, uniformly mixing, filtering, and canning to obtain the curing agent.

Technical Field

The invention relates to the technical field of printing ink, and particularly relates to photosensitive solder resist white oil and a preparation method thereof.

Background

Printed Circuit Boards (PCBs) are important electronic components and are generally obtained by coating a photocurable ink, drying, covering a mask plate, exposing, developing, etching, and peeling off a protective layer of the photocurable ink. The photo-curing printing ink forms a printing ink layer after being dried, and the printing ink layer can be subjected to cross-linking curing or degradation reaction to form a protective layer during exposure. However, the existing oil film has the problems of low heat resistance, yellowing resistance, leveling property, insufficient gloss and the like.

Disclosure of Invention

The invention aims to provide photosensitive solder resist white oil and a preparation method thereof, so as to solve the technical problems.

In order to achieve the purpose, the technical scheme of the invention is as follows:

in a first aspect, the photosensitive solder resist white oil provided by the invention comprises a main agent and a curing agent, wherein the main agent comprises the following components in parts by weight: 40.0-60.0 parts of maleic anhydride modified unsaturated polyester, 5.0-10.0 parts of photoinitiator, 15.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.2 parts of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-3.0 parts of fumed silica and 10.0 parts of diluent A0; the curing agent comprises the following components in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-9.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-4.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 4.0-8.0 parts of titanium dioxide, 2.0-4.0 parts of dibasic ester and 10.0 parts of diluent B0.

Preferably, the maleic anhydride modified unsaturated polyester is prepared from the following raw materials in parts by weight: 20-25 parts of maleic anhydride, 10-15 parts of styrene, 20-25 parts of glycidyl ether, 10-13 parts of dibasic ester, 0.5-1.5 parts of initiator, 0.1-0.3 part of catalyst, 0.2-0.4 part of polymerization inhibitor, 10-15 parts of monomer, 0.1-0.15 part of anti-aging agent, 8-12 parts of ethanol and 10-15 parts of hexahydrophthalic anhydride.

Preferably, the photoinitiator is selected from any one or more of photoinitiator ITX, photoinitiator TPO, and photoinitiator 819.

Preferably, the filler is selected from any one or more of barium sulfate, titanium dioxide, talcum powder, kaolin, calcium carbonate, bentonite and carbon black.

Preferably, the defoaming agent is selected from any one or more of defoaming agent KS-66, defoaming agent KS-603, defoaming agent KS-604 and defoaming agent KS-53.

Preferably, the diluent A is selected from any one of non-reactive diluent and reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of pentaerythritol tetraacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate and butanediol diacrylate.

Preferably, the main agent comprises the following components in parts by weight: 40.0-50.0 parts of maleic anhydride modified unsaturated polyester, 5.0-6.0 parts of photoinitiator, 23.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.0 part of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-1.2 parts of fumed silica and 0-10 parts of diluent A.

Preferably, the diluent B is selected from any one of a non-reactive diluent and a reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of pentaerythritol tetraacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate and butanediol diacrylate.

Preferably, the curing agent comprises the following components in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-8.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-3.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 5.0-8.0 parts of titanium dioxide, 2.0-3.0 parts of dibasic ester and 10.0 parts of diluent B0.

In a second aspect, the invention provides a method for preparing the photosensitive solder resist white oil according to the first aspect, which comprises the following steps:

(1) uniformly mixing maleic anhydride modified unsaturated polyester, a photoinitiator, a filling agent, a flatting agent, a defoaming agent, dibasic acid ester and fumed silica, grinding for 1-5 times, adding a diluent A, uniformly mixing, filtering and canning to obtain a main agent;

(2) uniformly mixing novolac epoxy resin, dipentaerythritol penta-hexaacrylate, hydroxyalkylamide, melamine, titanium dioxide and dibasic acid ester, grinding for 1-5 times, adding diluent B, uniformly mixing, filtering, and canning to obtain the curing agent.

Compared with the prior art, the invention has the beneficial effects that:

the main agent containing maleic anhydride modified unsaturated polyester and the curing agent are mixed and coated on a base material of a printed circuit board, when the mixture is exposed, a photoinitiator in an ink layer of an exposed part initiates a prepolymer (maleic anhydride modified unsaturated polyester) to perform polymerization reaction to obtain a polymer, and a protective layer with good adhesive force and hardness is formed under the compounding action of the novolac epoxy resin, the polymer, the filler and other components.

Detailed Description

The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

In a first aspect, the photosensitive solder resist white oil provided by the invention comprises a main agent and a curing agent, wherein the main agent comprises the following components in parts by weight: 40.0-60.0 parts of maleic anhydride modified unsaturated polyester, 5.0-10.0 parts of photoinitiator, 15.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.2 parts of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-3.0 parts of fumed silica and 10.0 parts of diluent A0; the curing agent comprises the following components in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-9.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-4.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 4.0-8.0 parts of titanium dioxide, 2.0-4.0 parts of dibasic ester and 10.0 parts of diluent B0.

In the embodiment, the weight ratio of the main agent to the curing agent is 3-4: 1.

In the embodiment, the maleic anhydride modified unsaturated polyester is prepared by adopting the following raw materials in parts by weight: 20-25 parts of maleic anhydride, 10-15 parts of styrene, 20-25 parts of glycidyl ether, 10-13 parts of dibasic ester, 0.5-1.5 parts of initiator, 0.1-0.3 part of catalyst, 0.2-0.4 part of polymerization inhibitor, 10-15 parts of monomer, 0.1-0.15 part of anti-aging agent, 8-12 parts of ethanol and 10-15 parts of hexahydrophthalic anhydride.

Further, the initiator is selected from one or more of benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, azobiscyclohexyl carbonitrile and 1,1' -azobis (cyclohexanecarbonitrile).

Further, the catalyst is selected from one or two of benzyl triphenyl phosphorus chloride and tetrabutyl titanate.

Further, the polymerization inhibitor is selected from one or more of tert-butyl catechol, copper naphthenate, hydroquinone, p-methoxyphenol, p-hydroxyanisole and methyl hydroquinone.

Further, the monomer is selected from one or more of hydroxyethyl methacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, hexanediol diacrylate, butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated ethoxylated pentaerythritol tetraacrylate.

Further, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 1098 and antioxidant 1024.

Further, the maleic anhydride modified unsaturated polyester is prepared by the following preparation method:

stirring and dissolving maleic anhydride, styrene, glycidyl ether and dibasic acid ester, adding an initiator, reacting for 4-6 hours at 120-130 ℃, cooling to 80-100 ℃, adding a catalyst, a polymerization inhibitor and a monomer, performing heat preservation reaction for 3-5 hours, adding an anti-aging agent, performing heat preservation reaction for 3-5 hours, measuring the acid value to be 6-7, adding the anti-aging agent, ethanol and hexahydrophthalic anhydride, performing heat preservation reaction for 3-4 hours, and cooling to obtain maleic anhydride modified unsaturated polyester.

In this embodiment, the photoinitiator is selected from any one or more of the photoinitiators ITX, TPO, 819.

In the present embodiment, the filler is selected from any one or more of barium sulfate, titanium dioxide, talc, kaolin, calcium carbonate, bentonite, and carbon black.

In this embodiment, the leveling agent is an organosilicon leveling agent.

In the embodiment, the defoaming agent is any one or more selected from defoaming agent KS-66, defoaming agent KS-603, defoaming agent KS-604 and defoaming agent KS-53.

In the present embodiment, the diluent a is selected from any one of a non-reactive diluent and a reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of pentaerythritol tetraacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate and butanediol diacrylate.

In this embodiment, the main agent includes, in parts by weight: 40.0-50.0 parts of maleic anhydride modified unsaturated polyester, 5.0-6.0 parts of photoinitiator, 23.0-30.0 parts of filler, 0.2-0.4 part of flatting agent, 0.8-1.0 part of defoamer, 2.0-4.0 parts of dibasic ester, 1.0-1.2 parts of fumed silica and 0-10 parts of diluent A.

In the present embodiment, the viscosity of the base compound is 100 to 300dpa · s.

In the present embodiment, the diluent B is selected from any one of a non-reactive diluent and a reactive diluent; the non-reactive diluent is selected from any one or more of ethanol, acetone and toluene; the reactive diluent is selected from one or more of pentaerythritol tetraacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate and butanediol diacrylate.

In this embodiment, the curing agent includes, in parts by weight: 8.0-10.0 parts of phenolic epoxy resin, 6.0-8.0 parts of dipentaerythritol penta-hexaacrylate, 2.0-3.0 parts of hydroxyalkylamide, 0.5-0.8 part of melamine, 5.0-8.0 parts of titanium dioxide, 2.0-3.0 parts of dibasic ester and 10.0 parts of diluent B0.

In the present embodiment, the viscosity of the curing agent is 50 to 60dpa · s.

In a second aspect, the invention provides a method for preparing the photosensitive solder resist white oil according to the first aspect, which comprises the following steps:

(1) uniformly mixing maleic anhydride modified unsaturated polyester, a photoinitiator, a filling agent, a flatting agent, a defoaming agent, dibasic acid ester and fumed silica, grinding for 1-5 times, adding a diluent A, uniformly mixing, filtering and canning to obtain a main agent;

(2) uniformly mixing novolac epoxy resin, dipentaerythritol penta-hexaacrylate, hydroxyalkylamide, melamine, titanium dioxide and dibasic acid ester, grinding for 1-5 times, adding diluent B, uniformly mixing, filtering, and canning to obtain the curing agent.

The following examples are described in detail.

It will be appreciated that the maleic anhydride-modified unsaturated polyesters used in the following examples were prepared by the following method:

weighing the following raw materials in parts by weight: 20 parts of maleic anhydride, 15 parts of styrene, 20 parts of glycidyl ether, 13 parts of dibasic ester, 1 part of benzoyl peroxide, 0.3 part of benzyl triphenyl phosphorus chloride, 0.4 part of tert-butyl catechol, 10 parts of hydroxyethyl methacrylate, 10100.1 parts of antioxidant, 8 parts of ethanol and 12.2 parts of hexahydrophthalic anhydride; stirring and dissolving maleic anhydride, styrene, glycidyl ether and dibasic ester, adding benzoyl peroxide, reacting at 125 ℃ for 5 hours, cooling to 90 ℃, adding benzyltriphenylphosphonium chloride, tert-butylcatechol and hydroxyethyl methacrylate, reacting for 4 hours under heat preservation, adding 60% of antioxidant 1010 in the formula amount, reacting for 3 hours under heat preservation, measuring the acid value to be 6-7, adding the rest of antioxidant 1010 in the formula amount, ethanol and hexahydrophthalic anhydride, reacting for 3.5 hours under heat preservation, and cooling to obtain the maleic anhydride modified unsaturated polyester.