CN1063269C

CN1063269C - One-component optical-imagery liquid soldering inhibitor and its preparation

Info

Publication number: CN1063269C
Application number: CN 97120324
Authority: CN
Inventors: 王尔鉴; 李妙贞; 何勇
Original assignee: Institute of Photographic Chemistry of CAS
Current assignee: Institute of Photographic Chemistry of CAS
Priority date: 1997-12-08
Filing date: 1997-12-08
Publication date: 2001-03-14
Anticipated expiration: 2017-12-08
Also published as: CN1184265A

Abstract

本发明属于印制电路板用涂覆材料领域，包括(重量百分数)复合型光反应性成膜树脂30～50%，丙烯酸酯交联剂及活性稀释剂15～30%，光敏引发剂2～6%，填料、颜料15～30%，助剂1～6%，溶剂10～20%。复合型光反应性成膜树脂是侧链含不饱和键和亲水基团树脂R1、主链含不饱和键树脂R2以及主链含不饱和键侧链含亲水基团树脂R3的树脂复合而成。其制法是在装有搅拌器的容器中，加入丙烯酸酯交联剂及活性稀释剂和溶剂，开动搅拌，加入光引发剂且全部溶解后再加入剩余组分，高速分散，使之混合，最终制成既经济又重现性好的本发明阻焊剂。The invention belongs to the field of coating materials for printed circuit boards, including (weight percent) 30-50% of composite photoreactive film-forming resin, 15-30% of acrylate crosslinking agent and reactive diluent, and 2-30% of photoinitiator. 6%, fillers and pigments 15-30%, additives 1-6%, solvents 10-20%. Composite photoreactive film-forming resin is a resin composite of resin R1 containing unsaturated bonds and hydrophilic groups in the side chain, resin R2 containing unsaturated bonds in the main chain, and resin R3 containing unsaturated bonds in the main chain and side chains containing hydrophilic groups. made. The preparation method is to add acrylate crosslinking agent, active diluent and solvent into a container equipped with a stirrer, start stirring, add photoinitiator and dissolve it completely, then add the remaining components, disperse at high speed, and mix them. Finally, the solder resist of the present invention with good economy and good reproducibility is produced.

Description

One-component optical-imagery liquid soldering inhibitor and method for making thereof

The invention belongs to used for printed circuit board coating material field, particularly relate to one-component optical-imagery liquid soldering inhibitor and method for making thereof.

In the Assembling Production process of electronic printed-circuit board; adopt group welder's skill for the welding of printed board more; the each point that it requires to need to weld on circuit; on remainder plate face; all to apply one deck welding resistance coating; coating can form after solidifying a kind ofly is not stained with scolder, and has high strength, high temperature resistant, high-insulativity and high adherence, and can be used as the coating material that permanent resist is used.

The solder resist kind of Chu Xianing is a silk-screen figure thermosetting solder resist the earliest, develops into light-cured type afterwards again.These kinds adopt the silk-screen graphical method, and low price is simple to operate, but resolution is lower, the only manufacturing of suitable single sided board.Along with the increase of integrated circuit memory capacity, the miniaturization of element, lightweight, printed circuit board is developed to dual platen and multiple-plate direction by single sided board, and this just has higher requirement to solder resist.Replace the silk-screen welding resistance with the liquid photo-imaging photosensitive solder resist at present, can satisfy printed board high density, high-resolution requirement, make product have higher quality and the reliability of Geng Gao, the Jap.P. spy opens clear 61-272 " ink component ", spy and opens the report that clear 60-208377 " welding resistance resin for printing ink constituent ", Japan's " surperficial real packing technique " 1994 6 phases of magazine article of 52 pages " liquid photoresistance solder flux " have this respect.

Current optical-imagery liquid soldering inhibitor is most popular to be two-component-type, promptly resin and hardening agent is divided and deposits, and allocates during use temporarily, cooperates the back product stabilities bad to overcome two kinds of materials, problem that can not long preservation.But still exist the poor reproducibility and the product that are artificially caused to cooperate the back to solidify the waste that brings during two kinds of material allotments because of making to too many or too much for use to produce.

The objective of the invention is to overcome the shortcoming of existing bi-component optical-imagery liquid soldering inhibitor, high density, the high resolving power of a kind of not only economy but also favorable reproducibility, the one-component optical-imagery liquid soldering inhibitor and the method for making thereof of high reliability are provided.

One-component optical-imagery liquid soldering inhibitor of the present invention comprise following component and each components contents following (unit: percent by weight):

(1). compound photoreactivity film-forming resin 30～50%

(2). acrylate cross linked dose and reactive diluent 15～30%

(3). photoinitiator 2～6%

(4). filler, pigment 15～30%

(5). auxiliary agent 1～6%

(6). solvent 10～20%

Wherein: acrylate cross linked dose accounts for 40%～95% of acrylate cross linked dose and reactive diluent general assembly (TW), and reactive diluent accounts for 5%～60%.

Described compound photoreactivity film-forming resin is that side chain contains unsaturated link and hydrophilic radical resin R ₁, main chain contains unsaturated link resin R ₂And main chain contains the unsaturated link side chain and contains hydrophilic radical resin R ₃Among any two kinds be composited, and shared percent by weight is respectively:

R ₁-R ₂, R wherein ₁Be 45%～55%, R ₂Be 45%～55%;

Or R ₂-R ₃, R wherein ₂Be 45%～55%, R ₃Be 45%～55%;

Or R ₁-R ₃, R wherein ₁Be 60%～70%, R ₃Be 30%～40%.

Acrylate cross linked dose is difunctional or multi-functional acrylate's class monomer; Reactive diluent is the simple function group acrylic ester monomer, difunctional or multi-functional acrylate's class are trimethylolpropane triacrylate for monomer crosslinked dose, the ethoxyquin trimethylolpropane triacrylate, the third oxidation trimethylolpropane triacrylate, pentaerythritol triacrylate, double pentaerythritol methacrylate, various alkane double methacrylates, the glycols double methacrylate is as the tripropylene glycol double methacrylate, ethylene glycol diacrylate, the propylene glycol double methacrylate, one condensed ethandiol double methacrylate, the tirethylene glycol double methacrylate, the hexanediol double methacrylate; Reactive diluent is an ethers simple function group acrylate, alkyl, aryl, cyclic group simple function group acrylate, hydroxyalkyl acrylates, hydroxyalkyl methacrylates; Filler, pigment are that mineral dust, talcum powder, lime carbonate, calcium sulphate, barium sulphate, titania and the phthalein mountain valley with clumps of trees and bamboo are green; Auxiliary agent is defoamer, surfactant, spreading agent, levelling agent, wetting agent, ultraviolet absorber, polymerization inhibitor, sagging inhibitor and promoter, and defoamer is: Byk-066, Byk-080, Byk-052, Byk-141 (German Byk company product), methyl-silicone oil 201,018; Levelling agent is: Byk-306,334,358, Byketol-Ok, Byketol-Special (German Byk company product), moral modest 435,455,466 (German DEUCHEM company product); Solvent is gylcol ether, propylene glycol ethers, glycol ether acetate, DGDE acetate and ketone compounds.

The method for making of one-component optical-imagery liquid soldering inhibitor:

(1). the method for making of compound photoreactivity film-forming resin

Compound photoreactivity film-forming resin is the key component that constitutes the liquid solder resist, requires to have good film forming, high-insulativity, high rigidity, good adhesion and high temperature resistant, chemical proofing.Therefore the present invention adopts epoxy resin, mandelic resin, styrene-propene acid resin copolymer, phenolics etc. as parent, by modification, introduces unsaturated link on resin backbone or side chain, makes it to have the photochemical reaction activity.The unsaturated link compound that contains commonly used has unsaturated carboxylic acid and ester class thereof, as butenoic acid (BUA), maleic acid (MAL), methacrylic acid (MA), acrylic acid (AA), cinnamic acid (CA), crylic acid hydroxy ester, methacrylic acid hydroxyl ester, methacrylic acid epoxy-ester etc.In order to realize the purpose of liquid alkali developing, in film-forming resin, also need introduce hydrophilic radical, as carboxyl, hydroxyl etc.Compound commonly used has: aliphatics and aromatic anhydride, dicarboxylic acids and hydroxyalkyl esters of unsaturated carboxylic acids etc.

The photoreactivity film-forming resin comprises that side chain contains unsaturated link and hydrophilic radical resin R ₁, main chain contains unsaturated link resin R ₂And main chain contains the unsaturated link side chain and contains hydrophilic radical resin R ₃Deng polytype, its method for making is:

A. side chain contains unsaturated link and hydrophilic radical resin R ₁Synthetic:

In that being housed, stirrer, condenser pipe, temperature take into account in the there-necked flask of wireway, add styrene (St), methyl methacrylate (MMA), hydroxy-ethyl acrylate (HEA) and solvent start and stir and feed nitrogen, logical nitrogen is after 20～30 minutes, under 80～100 ℃ of temperature, add polymerization initiator, reaction totally 5～6 hours in batches, and then the adding unsaturated acid anhydride, continue reaction and promptly got resin R in 3～4 hours ₁Wherein each material addition is:

By its molar weight, styrene: methyl methacrylate: hydroxy-ethyl acrylate: unsaturated acid anhydride=2.0: 1.0: 1.4: 1.0;

By its weight, the polymerization initiator addition accounts for 0.8%～1.0% of total monomer weight;

By its weight, solvent adding amount accounts for 35%～45% of total monomer weight.

B. main chain contains unsaturated link resin R ₂Synthetic:

In the there-necked flask that stirrer, condenser pipe, thermometer are housed, adding epoxide equivalent is the epoxy resin of 0.4～0.5 equivalent/100 grams, be heated to fusing, add by unsaturated fatty acid catalyzer, the mixed liquor that polymerization inhibitor is formed down at 80～90 ℃, adding the back reacted 5～7 hours down at 100～120 ℃, measuring acid number, is 10 to finish when following to acid number, must resin R ₂

Wherein each material addition is:

By its molar weight, epoxy resin: unsaturated fatty acid=0.9: 1.8;

By its weight, the addition of catalyzer accounts for 0.2%～0.3% of weight epoxy;

By its weight, the addition of polymerization inhibitor accounts for 0.15%～0.25% of weight epoxy.

C. main chain contains the unsaturated link side chain and contains hydrophilic radical resin R ₃Synthetic:

In the there-necked flask that stirrer, condenser pipe, thermometer are housed, adding epoxide equivalent is 0.4～0.5 equivalent/100 gram epoxy resin, heat fused adds by unsaturated fatty acid the mixed liquor that polymerization inhibitor and catalyzer are formed down at 90～100 ℃, adding the back reacted 5～7 hours down at 100～120 ℃, measure acid number, to acid number be 10 when following, be cooled to 80～90 ℃, add acid anhydrides again, react 2～4 hours resin R ₃

Wherein each material addition is:

By its molar weight, epoxy resin: unsaturated fatty acid: acid anhydrides=1.6: 3.0: 0.8;

By its weight, the addition of polymerization inhibitor accounts for 0.3%～0.45% of weight epoxy.

(2) side chain is contained unsaturated link and hydrophilic radical resin R ₁, main chain contains unsaturated link resin R ₂, main chain contains the unsaturated link side chain and contains hydrophilic radical resin R ₃Make compound photoreactivity film-forming resin and shared percent by weight is respectively by following cooperation:

R ₁-R ₂, R wherein ₁Be 45%～55%, R ₂Be 45%～55%;

R ₂-R ₃, R wherein ₂Be 45%～55%, R ₃Be 45%～55%;

R ₁-R ₃, R wherein ₁Be 60%～70%, R ₃Be 30%～40%.

During the photoreactivity film-forming resin was synthetic, polymerization initiator can adopt azoisobutyronitrile (AIBN) or benzoyl peroxide (BPO); Polymerization inhibitor can adopt MEHQ (MOP), p-dihydroxy-benzene (Hyd) etc.; Catalyzer adopts N, accelerine (DMA), tetramethyl ammonium chloride (TMAC), trimethyl benzyl amine (BTMA), benzyltrimethylammonium chloride (BMAC) etc.; Solvent gylcol ether commonly used such as glycol dimethyl ether etc., glycol ether acetate etc.

Acrylate cross linked dose and reactive diluent

Acrylate cross linked dose that the present invention selects for use is difunctional or multi-functional acrylate's class monomer.They with compound photoreactivity film-forming resin generation radical crosslinking polyreaction, generate the cured film that has than high crosslink density in photocuring reaction, give coating good mechanical and physical performance.Specifically have: trimethylolpropane triacrylate, the ethoxyquin trimethylolpropane triacrylate, the third oxidation trimethylolpropane triacrylate, pentaerythritol triacrylate, double pentaerythritol methacrylate, various alkane double methacrylates, glycols double methacrylate such as tripropylene glycol double methacrylate, ethylene glycol diacrylate, propylene glycol double methacrylate, a condensed ethandiol double methacrylate, tirethylene glycol double methacrylate, hexanediol double methacrylate etc.

Reactive diluent mainly is the simple function group acrylic ester monomer, in system resin is played diluting effect.Specifically have: ethers simple function group acrylate, alkyl, aryl, cyclic group simple function group acrylate such as acrylic acid tetrahydrofuran ester, isobornyl acrylate etc., hydroxyalkyl acrylates, hydroxyalkyl methacrylates such as hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxypropyl methyl acrylate or the like.

Wherein, acrylate cross linked dose of shared percent by weight is 40%～95%; Reactive diluent is 5%～60%.

Photoinitiator:

This is to cause the requisite composition of photochemical reaction, and consumption is few but very important.The photoinitiator that the present invention uses is the free radical type initiating agent, comprises two types:

A. arone/amine: as benzophenone, michaelis ketone, various replacement thioxanthones etc., they and aliphatics or aromatic nitrile base cooperate, and constitute initiator system.

B. photodestruciton type initiating agent:, I-651, I-184, I-149, I-1700, I-907, I-369 (Switzerland Ciba company) etc. are arranged specifically as styrax ethers, acetophenone derivs etc.

Filler, pigment

Be mechanical and physical performance and the processing characteristics of improving coating, and operation and the observation of being convenient to producers, the present invention need add a certain proportion of filler and pigment, and is green etc. as mineral dust, talcum powder, lime carbonate, calcium sulphate, barium sulphate, titania and the phthalein mountain valley with clumps of trees and bamboo.Solder resist of the present invention is green.

Auxiliary agent

For avoid optical-imagery liquid soldering inhibitor store and use in occur such as sedimentation, bubble, pin hole, grow dim, disadvantages such as be full of cracks, tangerine peel, need interpolation have the auxiliary agent of various functions to improve its overall performance.Auxiliary agent commonly used has defoamer, surfactant, spreading agent, levelling agent, wetting agent, ultraviolet absorber, polymerization inhibitor, sagging inhibitor and promoter or the like.

Specifically have:

Defoamer is as Byk-066, Byk-080, Byk-052, Byk-141, methyl-silicone oil 201,018 etc.;

Surfactant is as Tween series, Span series, Triton-X series etc.;

Spreading agent is as Disperbyk-110,161,163,181 (German Byk company product) etc.;

Levelling agent is as Byk-306,334,358, Byketol-Ok, Byketol-Special, moral modest 435,455,466;

Wetting agent is as moral modest DP-983, DP-981 (German DEUCHEM company product);

Ultraviolet absorber is as Tinuvin-384,1130,400 (Switzerland Ciba refine company product);

Polymerization inhibitor is as p-dihydroxy-benzene, 2,6-toluene di-tert-butyl phenol, MEHQ, benzotriazole;

Sagging inhibitor is as Disperbyk-170, and 166, Anti-TerraU (German Byk company product);

Promoter is as N, N dimethylamine yl benzoic acid ethyl ester, N, N dimethylamine yl benzoic acid isopentyl ester etc.

Solvent: the main diluting effect that rises in system.Solvent commonly used has gylcol ether such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether etc., propylene glycol ethers, glycol ether acetate, DGDE acetate and ketone compounds etc.

(3) preparation one-component optical-imagery liquid soldering inhibitor of the present invention, by weight percentage:

In the container of stirrer is housed, acrylate cross linked dose and the solvent of reactive diluent and 10～20% of adding 15～30% start stirring, add 2～6% photoinitiator then, after making it dissolving, add 30～50% compound photoreactivity film-forming resin more in turn, 15～30% filler, pigment and 1～6% auxiliary agent, high speed dispersion, make it to mix, being ground to fineness then on three-roller is 3～5 μ m, promptly gets one-component optical-imagery liquid soldering inhibitor.

Solder resist of the present invention is to be used to produce two-sided and novel solder resist material multilayer printed circuit board.

Advantage of the present invention:

The present invention is an one-component optical-imagery liquid soldering inhibitor, (1) it is exactly whole component integrators with the different of two-component-type maximum, need not allocate before the use, the problem of the artificial poor reproducibility that causes in the time of can avoiding allocating also can reduce product simultaneously and cooperate the back to solidify the waste that is brought because of making to too many or too much for use to produce.(2) the present invention has the advantage of optical-imagery liquid soldering inhibitor high density, high resolving power, high reliability.Has simultaneously the active and storage stability of very high photochemical reaction, good physical property and picture quality again.(3) the present invention adopts liquid alkali developing processing, saves solvent, reduces cost, reduces pollution, has bigger superiority than solvent develop.(4) use the present invention, do not need production equipment special, identical with the technological process of bi-component optical-imagery liquid soldering inhibitor.

Specifically set forth the present invention below in conjunction with embodiment

The photoreactivity film-forming resin synthesizes embodiment

Embodiment 1-R ₁Synthesizing of resin

Stirrer is being housed, condenser pipe, temperature is taken into account in 1000 milliliters of there-necked flasks of wireway, add 208g (2.0mol) styrene (St), 100g (1.0mol) methyl methacrylate (MMA), 162g (1.4mol) hydroxy-ethyl acrylate (HEA) and account for the glycol dimethyl ether of their monomer total amounts (percentage by weight) 40% (192g), start stirring, heat up, and feeding nitrogen, logical nitrogen is warming up to about 82 ℃ after 30 minutes, the azoisobutyronitrile (AIBN) that in batches adds 0.4% (2g), reacted 3 hours, add the azoisobutyronitrile (AIBN) of 0.4% (2g) again, continue reaction after 3 hours, add 98g (1.0mol) maleic anhydride (MAn) again, react and promptly got resin R in about 3.5 hours ₁

Embodiment 2-R ₂Synthesizing of resin

In 1000 milliliters of there-necked flasks that stirrer, condenser pipe, thermometer are housed, add 450g (1.8mol) bisphenol A epoxide resin, be heated to fusing, about 85 ℃, add down by 309g (3.6mol) methacrylic acid (MA), 0.9gN, the mixed liquor that accelerine (DMA) and 0.68g MEHQ (MOP) are formed adds the back and reacted about 5.5 hours down about 105 ℃, measures acid number, when acid number is that 10 following time reactions finish, resin R ₂

Embodiment 3-R ₃Synthesizing of resin

In 2000 milliliters of there-necked flasks that stirrer, condenser pipe, thermometer are housed, add 800g (3.2mol) novalac epoxy, heat fused, about 97 ℃, add 432g (6.0mol) acrylic acid (AA) down, 1.6g MEHQ (MOP) and 2.4g N, the mixed liquor that accelerine (DMA) is formed, adding the back reacted about 5.5 hours down about 110 ℃, measure acid number, when acid number is below 10, be cooled to 80 ℃, add 236g (1.6mol) phthalic anhydride (pA) again, continue reaction and got resin R in about 2.5 hours ₃

Embodiment 4-R ' ₃Synthesizing of resin

According to R ₃The synthetic method of resin replaces phthalic anhydride (pA) with 156.9g (1.6mol) maleic anhydride (MAn), can get R ' ₃Resin.

One-component optical-imagery liquid soldering inhibitor method for making embodiment

Embodiment 1.

In 2000 ml containers of stirrer are housed (percent by weight), add 160 gram (16%) trimethylolpropane triacrylates, 85 gram (8.5%) isobornyl acrylate, 120 gram (12%) ethylene glycol monomethyl ether, and moving the stirring, make it to mix, add 40 gram (4%) I-651 then, stirring and dissolving after treating all to dissolve, adds 220 gram (22%) R more in turn ₁Resin, 190 gram (19%) R ₂Resin, 150 restrains (15%) talcum powder, 18 gram (1.8%) phthalein mountain valley with clumps of trees and bamboos are green, 5 gram (0.5%) morals modest-466,5 restrain (0.5%) Byk-052,5 gram (0.5%) Disperbyk-161 and 2 restrain (0.2%) benzotriazoles, add the back high speed dispersion, mix, be about 4 μ m being ground to fineness on the three-roller again, promptly get 1000 gram one-component optical-imagery liquid soldering inhibitors.

Embodiment 2. pentaerythritol triacrylates 130 gram (13%) hydroxy-ethyl acrylates 170 gram (17%) ethylene glycol monomethyl ether 120 gram (12%) I-369 20 gram (2%) benzophenone 20 gram (2%) R ₂Resin 170 gram (17%) R ₃Resin 160 grams (16%)

Barium sulphate powder 130 grams (13%)

Green 20 grams (2%) of the phthalein mountain valley with clumps of trees and bamboo

Disperbyk-110 10 grams (1%)

Byk-141 18 grams (1.8%)

Byk-306 30 grams (3%)

Benzotriazole 2 gram (0.2%) compound methods are undertaken by embodiment 1, obtain 1000 gram one-component optical-imagery liquid soldering inhibitors.

Embodiment 3.

Pentaerythritol triacrylate 170 grams (17%)

Hydroxyethyl methylacrylate 130 grams (13%)

Ethylene glycol monomethyl ether 120 grams (12%)

I-149 35 grams (3.5%)

R ₁Resin 90 grams (9.5%)

R ₃Resin 205 grams (20.5%)

Talcum powder 196 grams (19.6%)

Green 21 grams (2.1%) of the phthalein mountain valley with clumps of trees and bamboo

Byk-052 5 grams (0.5%)

Disperbyk-163 7 grams (0.7%)

Modest-455 14 grams (1.4%) of moral

Embodiment 4.

Ethoxyquin trimethylolpropane triacrylate 97 grams (9.7%)

Hexanediol double methacrylate 43 grams (4.3%)

Acrylic acid tetrahydrofuran ester 10 grams (1.0%)

Ethylene glycol monomethyl ether 90 grams (9%)

I-907 35 grams (3.5%)

R ₂Resin 215 grams (21.5%)

R ₃Resin 235 grams (23.5%)

Talcum powder 210 grams (21%)

Green 19 grams (1.9%) of the phthalein mountain valley with clumps of trees and bamboo

Byk-052 6 grams (0.6%)

Disperbyk-161 15 grams (1.5%)

Byk-334 23 grams (2.3%)

Embodiment 5.

With 228 gram (22.8%) R ₂Resin and 222 gram (22.2%) R ₄Resin cooperates, and all the other are undertaken by embodiment 4, obtains 1000 gram one-component optical-imagery liquid soldering inhibitors.

Claims

1. A single-component photoimaging liquid solder resist, including acrylate crosslinking agent and diluent, photoinitiator, filler, pigment, auxiliary agent, solvent, is characterized in that the weight percentage of its component and component content is:

(1). Composite photoreactive film-forming resin 30-50%;

(2). Acrylate crosslinking agent and reactive diluent 15-30%;

(3).Photoinitiator 2～6%;

(4). Fillers and pigments 15-30%;

(5). Auxiliary 1~6%;

(6). Solvent 10-20%;

in:

The acrylate crosslinking agent accounts for 40%-95% of the total weight of the acrylate crosslinking agent and reactive diluent, and the reactive diluent accounts for 5%-60%;

The composite photoreactive film-forming resin is a side chain containing unsaturated bond and hydrophilic group resin R ₁ , a main chain containing unsaturated bond resin R ₂ and a main chain containing unsaturated bond side chain containing a hydrophilic group resin R ₃ Any two of them are compounded, and the weight percentages are:

R ₁ -R ₂ , wherein R ₁ is 45% to 55%, and R ₂ is 45% to 55%;

or R ₂ -R ₃ , wherein R ₂ is 45% to 55%, and R ₃ is 45% to 55%;

Or R ₁ -R ₃ , wherein R ₁ is 60%-70%, and R ₃ is 30%-40%.

2. The one-component photoimaging liquid solder resist according to claim 1, wherein the acrylate crosslinking agent is a bifunctional or multifunctional acrylate monomer; the reactive diluent is a monofunctional acrylate monomer.

3. The single-component photoimaging liquid solder resist as claimed in claim 2, characterized in that the cross-linking agent of the bifunctional or multifunctional acrylate monomer is trimethylolpropane triacrylate, ethoxylated trimethylol Propane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, various alkane diacrylates, glycol diacrylates.

4. The single-component photoimaging liquid solder resist as claimed in claim 2 is characterized in that said reactive diluent is ether monofunctional acrylate, alkyl, aryl, ring-based monofunctional acrylate, hydroxyalkyl acrylate , Hydroxyalkyl methacrylate.

5. The single-component photoimaging liquid solder resist according to claim 1, characterized in that the fillers and pigments are ore powder, talcum powder, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide and phthalocyanine green.

6. One-component photoimaging liquid solder resist as claimed in claim 1, characterized in that said auxiliary agent is defoamer, surfactant, dispersant, leveling agent, wetting agent, ultraviolet absorber, polymerization inhibitor , anti-settling agent and accelerator.

7. The single-component photoimaging liquid solder resist as claimed in claim 7, wherein the defoamer is: Byk-066, Byk-080, Byk-052, Byk-141, methyl silicone oil 201,018; The leveling agents are: Byk-306, 334, 358, Byketol-Ok, Byketol-Special, Deqian 435, 455, 466.

8. The single-component photoimaging liquid solder resist as claimed in claim 1, wherein said solvent is glycol ethers, propylene glycol ethers, glycol ether acetate, diethylene glycol ethyl ether acetate and ketone compounds .

9. A method for preparing a single-component photoimaging liquid solder resist, characterized in that:

(1). The preparation method of composite photoreactive film-forming resin,

a. The synthesis of resin R ₁ containing unsaturated bonds and hydrophilic groups in the side chain:

Add styrene, methyl methacrylate, hydroxyethyl acrylate and solvents to a three-neck flask equipped with a stirrer, condenser, thermometer and gas guide tube, start stirring and feed nitrogen gas for 20 to 30 minutes. At a temperature of 80-100°C, add polymerization initiators in batches, react for a total of 5-6 hours, then add unsaturated acid anhydride, and continue to react for 3-4 hours to obtain resin R ₁ , wherein the amount of each substance added is:

In terms of molar weight, styrene: methyl methacrylate: hydroxyethyl acrylate: unsaturated anhydride=2.0: 1.0: 1.4: 1.0;

Based on its weight, the amount of the polymerization initiator added accounts for 0.8% to 1.0% of the weight of the monomer;

By weight, the amount of solvent added accounts for 35% to 45% of the weight of the monomer;

b. Synthesis of resin _R2 containing unsaturated bonds in the main chain:

In a three-necked flask equipped with a stirrer, a condenser, and a thermometer, add epoxy resin with an epoxy equivalent of 0.4 to 0.5 equivalents/100 grams, heat until it melts, and add unsaturated fatty acids at 80 to 90 ° C. Catalyst, The mixed liquid composed of polymerization inhibitor is reacted at 100-120°C for 5-7 hours after the addition, and the acid value is measured, and the acid value is less than 10, and the resin _R2 is obtained;

Wherein each material adding amount is:

According to its molar weight, epoxy resin: unsaturated fatty acid=0.9: 1.8;

By weight, the amount of catalyst added accounts for 0.2% to 0.3% of the epoxy resin;

By weight, the amount of the polymerization inhibitor accounts for 0.15% to 0.25% of the epoxy resin;

c. Synthesis of resin R ₃ containing unsaturated bonds in the main chain and hydrophilic groups in the side chains:

In a three-necked flask equipped with a stirrer, a condenser, and a thermometer, add epoxy resin with an epoxy equivalent of 0.4-0.5 equivalent/100 g, heat and melt, and add unsaturated fatty acid and polymerization inhibitor at 90-100 ° C. Mixed solution composed of catalyst and catalyst, react at 100-120°C for 5-7 hours after adding, measure the acid value, when the acid value is below 10, cool down to 80-90°C, then add acid anhydride, react for 2-4 hours Obtain resin R ₃ ;

Wherein each material adding amount is:

According to its molar weight, epoxy resin: unsaturated fatty acid: acid anhydride=1.6: 3.0: 0.8;

By weight, the amount of the polymerization inhibitor accounts for 0.3% to 0.45% of the epoxy resin;

(2) The side chain containing unsaturated bond and hydrophilic group resin R ₁ , the main chain containing unsaturated bond resin R ₂ , the main chain containing unsaturated bond side chain containing hydrophilic group resin R ₃ according to the following coordination Composite photoreactive film-forming resin is made and the percentages by weight are respectively:

R ₁ -R ₂ , wherein R ₁ is 45% to 55%, and R ₂ is 45% to 55%;

R ₂ -R ₃ , wherein R ₂ is 45% to 55%, and R ₃ is 45% to 55%;

R ₁ -R ₃ , wherein R ₁ is 60% to 70%, and R ₃ is 30% to 40%;

(3) prepare the single-component photoimaging liquid solder resist of the present invention, by weight percentage:

In a container equipped with a stirrer, add 15-30% acrylate crosslinking agent and reactive diluent and 10-20% solvent, start stirring, then add 2-6% photoinitiator to dissolve it , then sequentially add 30-50% composite photoreactive film-forming resin, 15-30% fillers, pigments and 1-6% additives, disperse at high speed, mix them evenly, and then grind them on a three-roller machine until The fineness is 3-5 μm, that is, a single-component photoimaging liquid solder resist.