CN100469843C - Liquid photosensitive ink and applied in printing circuit board - Google Patents
Liquid photosensitive ink and applied in printing circuit board Download PDFInfo
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- CN100469843C CN100469843C CN 200710073879 CN200710073879A CN100469843C CN 100469843 C CN100469843 C CN 100469843C CN 200710073879 CN200710073879 CN 200710073879 CN 200710073879 A CN200710073879 A CN 200710073879A CN 100469843 C CN100469843 C CN 100469843C
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Abstract
This invention relates to a liquid form, sensitization, and soldering-proof ink. According to weight, it includes: 35 to 75% light sensitivity alkali fusion resin, 0.5 to 20% photoinitiator, 5 to 49% heat convertible resin, 10 to 54% diluter, 5 to 49% filler, 0 to 30% pigment, 0 to 10% accessory ingredient; the light sensitivity alkali fusion resin obtained by follow method: heat the mixture of dissolubility phenol formaldehyde resin( phenol hydroxyl value is 300 to 600), unsaturation alkenyl acid glycidelipid, solvent, catalyzer and polymerization inhibitor till phenol hydroxyl value stable; mole ratio between epoxy of unsaturation alkenyl acid glycidelipid and phenolic hydroxyl group of phenol formaldehyde resin is 0.2 to 0.8 :1; weight percentage of solvent and phenol formaldehyde resin is 25% to 150%; weight percentage of catalyzer and phenolic is 0.01 to 5%; weight percentage of polymerization inhibitor and phenol formaldehyde resin is 0.01 to 1%.
Description
Technical field
The present invention relates to a kind of printing circuit board printing ink, relate in particular to a kind of liquid photosensitive welding resistant printing ink and in the application of printing circuit board.
Background technology
Circuit-board industry develops to high-performance, high-precision two-sided, multilayer printed circuit board and flexible circuit board direction, and it is quite general to use liquid photosensitive welding resistant printing ink to print high-density, high precision, high-performance circuit board.
After 2007, along with RoHS (The Restriction of the use of certain Hazardoussubstances in Electnical and Electronic Equipment, use some objectionable impurities instruction about restriction in electronic electric equipment) enforcement of environmental protection ban, the spray tin treatment technology of printed circuit board pad terne metal will be stepped down and technology such as chemical nickel plating gold, chemical plating stannum.
In technology such as chemical nickel plating gold, chemical plating stannum, need to adopt liquid photosensitive welding resistant printing ink, be used to reserve through hole to be welded on the plate and weldering footpath (pad) thereof, all circuits and copper face are all covered the short circuit that causes when preventing wave soldering; Prevent that moisture and various electrolytical infringement from making the circuit oxidation and endangering electrical properties, and prevent that external mechanical wounding is with retaining plate face good insulation performance etc.
Liquid photosensitive welding resistant printing ink is a kind of photo-thermal curing liquid alkali developing resin combination, includes photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and other auxiliary agent.The photosensitivity alkali soluble resin of liquid photosensitive welding resistant printing ink is with phenol aldehyde type epoxy resin and unsaturated carboxylic acid reaction, again with composition saturated or that the unsaturated acid anhydride reactant obtains.Though this composition excellent heat resistance owing to contain a large amount of ester bonds, is easy to generate the decline of intensity under the condition of acidic chemical nickel gold solution and chemical plating stannum liquid medicine 85 degree.Therefore can't satisfy the requirement of chemical nickel plating gold and chemical plating stannum.
Prior art with hydroxyl unsaturated compound reacted composition, obtains the photosensitivity alkali soluble resin also with vinylbenzene and acid anhydride copolymer, but can't satisfy the requirement of chemical nickel plating gold and chemical plating stannum equally.
Prior art also with bisphenol-type epoxy resin and unsaturated monocarboxylic reaction, with saturated or unsaturated acid anhydride reactant, obtains the photosensitivity alkali soluble resin again.There is same shortcoming in the liquid photosensitive welding resistant printing ink of its composition; And anti-scolding tin thermal shocking is not enough, thereby has limited the application of this printing ink at rigid printed circuit boards, and sticking power, thermotolerance are relatively poor too.
Therefore, there is defective in prior art, needs to improve.
Summary of the invention
The object of the present invention is to provide a kind of liquid photosensitive welding resistant printing ink that satisfies chemical nickel plating gold and chemical plating stannum requirement and in the application of printing circuit board, the decline that under the condition of acidic chemical nickel gold solution and chemical plating stannum liquid medicine 85 degree, is not easy to produce intensity, and anti-scolding tin thermal shocking is strong, and sticking power, thermotolerance are better.
Technical scheme of the present invention is as follows:
A kind of liquid photosensitive welding resistant printing ink, wherein, it comprises photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and auxiliary agent; Wherein, the weight percent of each component is: the molten resin content of photosensitive bases is 35～75%, photoinitiator levels is 0.5～20%, thermosetting resin content is 5～49%, amount of diluent is 10～54%, filler content is 5～49%, and pigment content is 0～30%, and auxiliary agent content is 0～10%;
Wherein, described photosensitivity alkali soluble resin is made by following method: adding the phenol hydroxyl value in reactor is the buck resol resin of 300-600, unsaturated thiazolinyl acid glycidyl ester, solvent, catalyzer, stopper, be heated to 85-130 degree centigrade react to the phenol hydroxyl value stable till;
Wherein, the phenolic hydroxyl group mole ratio of the epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and described resol is 0.2-0.8; The weight percent of described solvent and described resol is 25% to 150%; The weight percent of described catalyzer and described resol is 0.01 to 5%; The weight percent of described stopper and described resol is 0.01 to 1%.
Described liquid photosensitive welding resistant printing ink, wherein, described unsaturated thiazolinyl glycidyl ester is glycidyl methacrylate, glycidyl acrylate or both miscellanys; Described solvent is durene, dimethylbenzene, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol monobutyl ether acetate, dipropylene glycol ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate or its miscellany; Described catalyzer is triphenyl phosphorus, antimony triphenyl, N, accelerine, N, N-dimethyl benzylamine, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, sodium hydroxide or potassium hydroxide; Described stopper is Resorcinol, p methoxy phenol, 2,5-dimethyl Resorcinol, 1,4-naphthalenediol or its miscellany.
Described liquid photosensitive welding resistant printing ink, wherein, the weight percent of described catalyzer and described resol is 0.5-2.5%; The weight percent of described stopper and described resol is 0.02% to 0.2%.
Described liquid photosensitive welding resistant printing ink, wherein, the photosensitivity alkali soluble resin to making also adds saturated acid anhydrides or unsaturated acid anhydride, be heated to 85-130 degree centigrade react to acid number stable till; Wherein, the weight percent of saturated acid anhydrides or unsaturated acid anhydride and described resol is below 40%.
Described liquid photosensitive welding resistant printing ink, wherein, described saturated acid anhydrides or unsaturated acid anhydride are Tetra hydro Phthalic anhydrides, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride.
Described liquid photosensitive welding resistant printing ink, wherein, the product that the hybrid reaction that described buck resol resin is A and B obtains; Wherein, A is formaldehyde, phenyl aldehyde or both miscellanys, and B is phenol, sylvan or both miscellanys; And described buck resol resin has following constitutional features:
R wherein
1Be C
6H
5Or H, R
2Be H or CH
3
Described liquid photosensitive welding resistant printing ink, wherein, the weight percent of each component is: the molten resin content of photosensitive bases is 15～60%, photoinitiator levels is 0.5～15%, thermosetting resin content is 5～20%, and amount of diluent is 15～45%, and filler content is 10～49%, pigment content is 0～15%, and auxiliary agent content is 0～5%.
A kind of liquid photosensitive welding resistant printing ink wherein, in printing circuit board, adopts liquid photosensitive welding resistant printing ink as solder resist in the application of printing circuit board; Wherein, described liquid photosensitive welding resistant printing ink comprises photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and auxiliary agent; Wherein, the weight percent of each component is: the molten resin content of photosensitive bases is 35～75%, photoinitiator levels is 0.5～20%, thermosetting resin content is 5～49%, amount of diluent is 10～54%, filler content is 5～49%, and pigment content is 0～30%, and auxiliary agent content is 0～10%;
Wherein, described photosensitivity alkali soluble resin is made by following method: adding the phenol hydroxyl value in reactor is the buck resol resin of 300-600, unsaturated thiazolinyl acid glycidyl ester, solvent, catalyzer, stopper, be heated to 85-130 degree centigrade react to the phenol hydroxyl value stable till;
Wherein, the phenolic hydroxyl group mole ratio of the epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and described resol is 0.2-0.8; The weight percent of described solvent and described resol is 25% to 150%; The weight percent of described catalyzer and described resol is 0.01 to 5%; The weight percent of described stopper and described resol is 0.01 to 1%;
And described buck resol resin is the mixture of A and B; Wherein, A is formaldehyde, phenyl aldehyde or both miscellanys, and B is phenol, sylvan or both miscellanys; And described buck resol resin has following constitutional features:
R wherein
1Be C
6H
5Or H, R
2Be H or CH
3
Described liquid photosensitive welding resistant printing ink is in the application of printing circuit board, and wherein, described unsaturated thiazolinyl glycidyl ester is glycidyl methacrylate, glycidyl acrylate or both miscellanys; Described solvent is durene, dimethylbenzene, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol monobutyl ether acetate, dipropylene glycol ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate or its miscellany; Described catalyzer is triphenyl phosphorus, antimony triphenyl, N, accelerine, N, N-dimethyl benzylamine, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, sodium hydroxide or potassium hydroxide; Described stopper is Resorcinol, p methoxy phenol, 2,5-dimethyl Resorcinol, 1,4-naphthalenediol or its miscellany.
Described liquid photosensitive welding resistant printing ink is in the application of printing circuit board, wherein, the weight percent of each component is: the molten resin content of photosensitive bases is 15～60%, photoinitiator levels is 0.5～15%, thermosetting resin content is 5～20%, and amount of diluent is 15～45%, and filler content is 10～49%, pigment content is 0～15%, and auxiliary agent content is 0～5%.
Adopt such scheme, the invention solves not water-disintegrable and the defective of pressure kettle steam and the problem of not anti-scolding tin thermal shocking of acid resistance such as phenolic aldehyde epoxy composite, bisphenol type epoxy composite, mandelic resin composition printing ink, provide cured film hardness height, cure shrinkage little, sticking power is good, thermotolerance is strong, takes into account photosensitivity and development, the well balanced liquid photosensitive welding resistant printing ink of anti-scolding tin thermal shocking simultaneously.
Description of drawings
Fig. 1 is a buck resol resin structure iron of the present invention.
Embodiment
Below preferred embodiment of the present invention is described in detail.
A kind of liquid photosensitive welding resistant printing ink provided by the invention is a kind of photo-thermal curing liquid alkali developing resin combination, and it comprises photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and auxiliary agent.
Wherein, described photosensitivity alkali soluble resin is made by following method: adding the phenol hydroxyl value in reactor is the buck resol resin of 300-600, unsaturated thiazolinyl acid glycidyl ester, solvent, catalyzer, stopper, be heated to 85-130 degree centigrade react to the phenol hydroxyl value stable till;
Wherein, the phenolic hydroxyl group mole ratio of the epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and described resol is 0.2-0.8; The weight percent of described solvent and described resol is 25% to 150%; The weight percent of described catalyzer and described resol is 0.01 to 5%; Be preferably 0.5-2.5%; The weight percent of described stopper and described resol is 0.01 to 1%, is preferably 0.02% to 0.2%.
Described unsaturated thiazolinyl glycidyl ester can be glycidyl methacrylate, glycidyl acrylate or both miscellanys.
Described solvent can be durene, dimethylbenzene, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol monobutyl ether acetate, dipropylene glycol ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate etc., or the miscellany of two or more above-claimed cpd arbitrarily.For example described solvent can be the miscellany of durene, dimethylbenzene and ethylene glycol ether acetate.
Described catalyzer can be triphenyl phosphorus, antimony triphenyl, N, accelerine, N, N-dimethyl benzylamine, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, sodium hydroxide or potassium hydroxide etc.; It also can be any miscellany of two or more above-claimed cpd.
Described stopper is Resorcinol, p methoxy phenol, 2,5-dimethyl Resorcinol, 1,4-naphthalenediol etc., or its miscellany.For example described stopper is the miscellany of Resorcinol, p methoxy phenol and 2.5-dimethyl Resorcinol.
After making the photosensitivity alkali soluble resin, can also add saturated acid anhydrides or unsaturated acid anhydride, be heated to 85-130 degree centigrade react to acid number stable till; The photosensitivity alkali soluble resin that obtains liquid photosensitive welding resistant printing ink of the present invention thus and adopted.Wherein, the weight percent of saturated acid anhydrides or unsaturated acid anhydride and described resol is below 40%, in general, can be about 20%-35%.
Wherein, described saturated acid anhydrides or unsaturated acid anhydride can be Tetra hydro Phthalic anhydrides, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or the like.
Described a kind of buck resol resin is that a kind of of constitutional features shown in Figure 1 or their miscellany are arranged.Described buck resol resin is that A mixes with B, under acidic conditions, and the 75-100 degree centigrade of product that reaction obtained in 2-4 hour; Wherein, A is formaldehyde, phenyl aldehyde or both miscellanys, and B is phenol, sylvan or both miscellanys; Acid can be adopted hydrochloric acid, sulfuric acid etc., and the pH value can be between 2.5 to 6, preferably between 4.1 to 4.5; The concrete preparation method of buck resol resin belongs to prior art, does not give unnecessary details at this.
For example, adding the phenol hydroxyl value in reactor is buck resol resin 200 grams of 300-600, glycidyl acrylate 30-120 gram, 2-Butoxyethyl acetate 200g, triphenyl phosphorus 1 gram, add Resorcinol 0.5g again, be heated to 85-130 degree reaction 15 hours, obtain stable phenol hydroxyl value to measuring; Add O-phthalic base acid anhydrides 40-60 gram, 85-130 ℃ was reacted 6 hours, obtained stable acidity to measuring, and promptly obtained the molten resin solution of described photosensitive bases.
Described liquid photosensitive welding resistant printing ink, the weight percent of each component is in the said composition:
The molten resin content of photosensitive bases is 35-75%;
Photoinitiator levels is 0.5-20%;
Thermosetting resin is to contain or do not contain resin other solidifying agent, that contain two and above epoxy group(ing) in molecule, and its content is 5-49%;
Thinner is to comprise solvent and at least a photosensitivity monomer, and its content is 10-54%;
Filler is various inorganic or organic stopping composition, and its content is 5-49%;
Pigment is selected different pigment according to the actual color needs, also can not add any pigment, and its content is 0-30%;
Other auxiliary agent, comprise can be singly with flow agent, the defoamer that also can merge use, adhere to the promotion oxidation inhibitor, also can not use any auxiliary agent, its content is 0-10%.
The preferred weight percent of each component is: the photosensitivity alkali soluble resin is 40-60%, and light trigger is 0.5-15%, and thermosetting resin is 5-20%, and thinner is 15-45%, and filler is 10-49%, and pigment is 0-15%, and auxiliary agent is 0-5%.
According to described liquid photosensitive welding resistant printing ink, the present invention also provides a kind of printed circuit board, scribbles liquid photosensitive welding resistant printing ink of the present invention on circuit card, has just constituted a kind of novel welding resistance circuit card.
Embodiment 1:
At first synthetic photosensitivity alkali soluble resin, adding phenol hydroxyl value is 465 buck resol resin (the green industry 30H of company limited that moulds of Weihai, Shandong gold) 200g in reactor, 2-Butoxyethyl acetate 200 grams, glycidyl acrylate 80 grams, triphenyl phosphorus 1g, be warming up to 90 ℃～130 ℃ reactions 24 hours to the phenol hydroxyl value less than 130, obtain solid content and be 58% light yellow resin solution (A).
In fact, the reaction times can shorten, and the present invention is also unrestricted to this, only need react to the phenol hydroxyl value is stable to get final product.For other condition, for example the phenol hydroxyl value of buck resol resin can be 300,320,350,400,450,500,550,580,600 etc., its consumption can be 150g, 180g, 200g, 225g, 240g, 250g or the like, unsaturated thiazolinyl acid glycidyl ester can be 60g, 70g, 80g, 90g, 100 grams etc., 2-Butoxyethyl acetate can be 150g, 180g, 200g, 220g, 240g, 250g or the like, triphenyl phosphorus can be 0.5g, 0.6g, 0.7g, 0.8g, 1g, 1.2g, 1.3g, 1.4g, 1.5g etc., Resorcinol can be 0.4g, 0.45g, 0.5g, 0.55g, 0.6g etc., only need satisfy the epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and the phenolic hydroxyl group mole ratio of described resol is that 0.2-0.8 gets final product, be preferably 0.4-0.6.
Prepare welding resistance printing ink then, get the molten resin solution of above-mentioned synthetic photosensitive bases (A) 100g, light trigger 907 (Ciba company light trigger) 10g, thermosetting resin: Dyhard RU 100 1g, E44 Resins, epoxy 15g, thinner: DPHA (dipentaerythritol acrylate) 6g, 150# (durene) solvent 8g, filler talcum powder (less than 2um) 15g, pigment: phthalocyanine green 1g, auxiliary agent: defoamer 0.5g.
Above-mentioned materials is mixed, and high speed dispersion 10 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink with three-roll grinder.
Embodiment 2:
Adding phenol hydroxyl value is 400 linear phenol formaldehyde resin (the rich printed material of Jiangyin, Jiangsu Kang Rong company limited 201) 200g in reactor, 2-Butoxyethyl acetate 200 grams, glycidyl acrylate 80 grams, triphenyl phosphorus 1g, be warming up to 90 ℃-130 ℃ the reaction 24 hours to the phenol hydroxyl value less than 100, it is that 60 solid contents are 62% light yellow resin solution (B) that the 50 gram 80-120 degree reactions of adding Tetra hydro Phthalic anhydride obtained acid number in 6 hours, wherein, the consumption of O-phthalic base acid anhydrides can be 40,42,45,50,55,58,60 grams etc., can obtain light yellow resin solution (B), the present invention is also unrestricted to this.When described photosensitivity alkali soluble resin adopted following method to obtain: adding phenol hydroxyl value was 450 buck resol resin 200 grams in reactor, unsaturated thiazolinyl acid glycidyl ester 80 grams, 2-Butoxyethyl acetate 200g, triphenyl phosphorus 1 gram, Resorcinol 0.5g, be heated to 95～130 degrees centigrade of reactions, until the phenol hydroxyl value less than 125; The better consumption of O-phthalic base acid anhydrides is 50g.
The resin liquid (B) that obtains is replaced photosensitive resin composition (A) resin solution among the embodiment 1, make welding resistance printing ink with embodiment 1 identical method.
Embodiment 3:
Adding phenol hydroxyl value is 450 linear ortho-cresol formaldehyde resin (company's 214 resins are advanced in Shanghai greatly) 200g in reactor, 2-Butoxyethyl acetate 200 grams, glycidyl acrylate 80 grams, triphenyl phosphorus 1g, be warming up to 90 ℃-130 ℃ reactions 24 hours to the phenol hydroxyl value less than 130, obtain solid content and be 58% light yellow resin solution (C)
The resin solution (C) that obtains is replaced photosensitive resin composition (A) resin solution among the embodiment 1, make welding resistance printing ink with embodiment 1 identical method.
Comparative example 1
In reactor, add 200 gram F48 Resins, epoxy (Wuxi resin processing plant) (epoxy mole number 240), add 200g butyl glycol ether amyl acetate, 0.5 gram Resorcinol, 57.6 gram vinylformic acid, 2 gram N, N-dimethylbenzyl ammonia was in 90 ℃ of reactions 20 hours, measure acid number less than 5, add 90 ℃ of reactions of Tetra hydro Phthalic anhydride 82 grams 6 hours, obtaining acid number is 61, and solid content is 63% shallow yellow transparent solution (D).
The resin solution (D) that obtains is replaced photosensitive resin composition (A) resin solution among the embodiment 1, make welding resistance printing ink with embodiment 1 identical method.
Comparative example 2
In reactor, add o-cresol formaldehyde epoxy resin 200 gram (epoxy mole number 250) (Wuxi resin processing plant products), add the 200g ethylene glycol ether acetate, 0.5g Resorcinol, 57.6 gram vinylformic acid, 2 gram N, 90 ℃ of reactions of N-dimethylbenzyl ammonia 20 hours, measure acid number less than 5, add Tetra hydro Phthalic anhydride 82g, 90 ℃ were reacted 6 hours, obtaining acid number is 61, and solid content is 63% shallow yellow transparent solution (E).
The resin solution (E) that obtains is replaced photosensitive resin composition (A) resin solution among the embodiment 1, make welding resistance printing ink with embodiment 1 identical method.
Comparative example 3
In reactor, add bisphenol A type epoxy resin 200 gram (E20 resins, epoxy mole number 500) (Wuxi resin processing plant product) adds the 200g ethylene glycol ether acetate, 28.8 gram vinylformic acid, 0.5 gram Resorcinol, 2 gram N, N-dimethylbenzyl ammonia temperature is controlled at 90-95 ℃ of reaction 20 hours, measures acid number less than 5, add Tetra hydro Phthalic anhydride 82g, 90 ℃ were reacted 6 hours, and obtaining acid number is 61, and solid content is 63% shallow yellow transparent solution (F).
The resin solution (F) that obtains is replaced photosensitive resin composition (A) resin solution among the embodiment 1, make welding resistance printing ink with embodiment 1 identical method.
For printing ink of the present invention in the comparing embodiment and the prior art printing ink in the comparative example, now measure touch dry (preliminary drying drying property), photosensitivity, development, tack, anti-scolding tin thermal shocking, acid resistance, alkali resistance, the flexibility of each printing ink in the following method, and will the results are shown in table 1 and compare.
(1), gives the baking drying property
With stencil with the welding resistance printing ink that makes, being printed on the cleaning exsiccant has made on the wiring board of condactive pattern, in 75 ℃ baking oven, give and took out cold in dry 20 minutes to room temperature, cover exposure Fei East-Roman-Empire (being the film) egative film, vacuumize exposure 60 seconds in exposure machine, the impression that takes out inspection printing ink is with the complexity that Fei East-Roman-Empire takes off.
Evaluation method is as follows: ink film does not have impression ， Fei East-Roman-Empire easily to take off to excellent fully; Ink film have slight impression ， Fei East-Roman-Empire to take off easily and not Zhan Fei East-Roman-Empire for good; Ink film has obvious impression ， Fei East-Roman-Empire to be difficult to take off and during Zhan Fei East-Roman-Empire is not; Ink film Zhan Fei East-Roman-Empire is for poor.
(2), development
With stencil the welding resistance printing ink that makes is coated on the cleaning exsiccant wiring board substrate, make sample board, each 6 on routine model is put into 75 degree constant temperature ovens and is toasted, kind was taken out one from baking oven in per 20 minutes, carry out development operation then, development conditions is: 0.1-0.5%NaOH (sodium hydroxide) aqueous solution, and 30 ℃ of liquid temperature, spray pressure is 1-3kg/cm
2
Evaluation method:
Give baking and can develop in 40 minutes totally, can not develop clean fully in 60 minutes for poor; Give baking and can develop in 60 minutes totally, can not develop fully in 80 minutes totally is; Give baking and can develop in 80 minutes totally, can not develop clean fully in 100 minutes for good; Gave baking 100 minutes and can develop clean for more time for excellent.
(3), photosensitivity
With stencil the welding resistance printing ink that makes is coated on the cleaning exsiccant wiring board substrate, 6 of each example coating sample boards place 75 ℃ of constant temperature ovens, give dry 30 minutes, be placed on the ink film with 21 rank exposure guide rules and expose, so to develop by the condition in the development (2).Be as the criterion as giving exposure energy with residual ink film 9 lattice of exposure guide rule, make an appraisal then.
Evaluation method is as follows:
Residual 9 lattice of exposure back development ink film need luminous energy less than 500mj/cm
2For excellent;
Residual 9 lattice of exposure back development ink film need luminous energy greater than 500mjcm
2Less than 600mj/cm
2For very;
Residual 9 lattice of exposure back development ink film need luminous energy greater than 600mj/cm
2Less than 700mj/cm
2For in;
Residual 9 lattice of exposure back development ink film need luminous energy greater than 700mj/cm
2For poor.
(4), sticking power
With stencil the welding resistance printing ink that makes is coated on the cleaning exsiccant wiring board, makes model, 75 ℃ of this plates
Baking oven baking 30 minutes gives residual 9 lattice of exposure imaging (by the condition in the development 2) ink film institute energy requirement respectively and exposes, and develops then, places this model 150 ℃ baking oven to toast 1 hour again, makes test sample plate.Adopt a stroke lattice adhesive tape method that model sticking power is tested.
Appraisal procedure: do not come off fully for excellent, drawing a ruling limit has and comes off on a small quantity for very, has more than 1 lattice to come off for poor.
(5), anti-scolding tin thermal shocking
Test sample plate is made identical with sticking power (4) test sample plate.
Testing method: test sample plate is sprayed the rosin soldering flux, place 270 ℃ of molten molten scolding tin to soak then 30 seconds, take out totally with the trieline cleaning, air-dry, visual detection.
Appraisal procedure: without any change (nondiscoloration, do not come off, do not swell) for excellent, change (variable color, come off, swell) be poor.
(6), acid resistance
Test sample plate is made identical with sticking power (4) test sample plate.
Testing method: test sample plate is soaked in the 10%H2SO4 aqueous solution, and temperature is 25 ℃, half an hour, takes out and washes totally, dries up.
Appraisal procedure: without any changing (nondiscoloration, do not come off, do not swell) for excellent, otherwise for poor.
(7), alkali resistance
Test sample plate is made identical with sticking power (4) test sample plate.
Testing method: test sample plate is soaked in the 10%NaOH aqueous solution, and temperature is 25 ℃, half an hour, takes out and cleans, dries up.
Appraisal procedure: excellent without any being changed to, change to poor.
(8), hydrolytic resistance
Test sample plate is made identical with sticking power (4) test sample plate.
Testing method: test sample plate is soaked in the aqueous sulfuric acid that pH value is 4-5, and temperature is 85 ℃, one hour, takes out and washes totally, dries up.
Appraisal procedure: without any changing (nondiscoloration, do not come off, do not swell) for excellent, otherwise for poor.
The contrast of the comparative example of embodiments of the invention and prior art is as shown in table 1.
The contrast of the comparative example of table 1 embodiments of the invention and prior art
From the result of table 1 as seen, in the embodiment of the invention owing to used the photosensitive alkali soluble resins of band phenolic hydroxyl group, the every performance of the light sensitive anti-solder ink of preparation is excellent, compare with the printing ink that the photosensitive alkali soluble resins of the carboxyl that uses in the comparative example obtains, because its thermofixation stage is the crosslinking reaction that is become ester by carboxyl with epoxy reaction, therefore hydrolytic resistance is poor, need can not to be applied to the manufacturing of the gold-plated circuit card of chemical plating stannum and chemical nickel plating.And the photosensitive composition thermofixation that obtains of the present invention is the crosslinking reaction that is become ether by phenolic hydroxyl group with epoxy reaction, good hydrolytic resistance is arranged, not only can be applicable to the manufacturing of general spray tin circuit card, and can be applicable to the manufacturing of the circuit card of chemical plating stannum and chemical nickel plating chemical gilding.
Compare as seen with comparative example 3, the composition that does not have methylolated bisphenol-type epoxy resin to obtain that comparative example 3 adopts is relatively poor in the anti-scolding tin thermal shocking of photosensitivity, need can not be applied to the circuit card manufacturing of anti-scolding tin thermal shocking.
For several embodiment liquid photosensitive welding resistant printing ink of the present invention is specifically described again below.Following solvent is example with the 2-Butoxyethyl acetate, and unsaturated thiazolinyl acid glycidyl ester is example with the glycidyl acrylate, and catalyzer is example with the triphenyl phosphorus, and stopper is example with the Resorcinol; Saturated acid anhydrides or unsaturated acid anhydride are example with the Tetra hydro Phthalic anhydride; Each particular compound of the present invention includes but not limited to above-mentioned example.
At first synthetic photosensitivity alkali soluble resin, adding phenol hydroxyl value is 300 buck resol resin 100g in reactor, 2-Butoxyethyl acetate 25g, glycidyl acrylate 15g, triphenyl phosphorus 0.01g adds Resorcinol 0.5g again, is warming up to 100 ℃ of reactions 24 hours, to the phenol hydroxyl value stable till, obtain light yellow resin solution G.Time can prolong or shorten, and only need react completely gets final product, and obtains stable phenol hydroxyl value by mensuration and gets final product, and for example, the phenol hydroxyl value is less than 180.Also can add Tetra hydro Phthalic anhydride 40g again and after 130 degrees centigrade of complete reactions, obtain light yellow resin solution G1, stablize and judge and react completely by measuring acid number to light yellow resin solution G.
Perhaps in reactor, add the phenol hydroxyl value and be 320 buck resol resin 100g, 2-Butoxyethyl acetate 50g, glycidyl acrylate 65g, triphenyl phosphorus 5g, add Resorcinol 0.01g again, be warming up to 90 ℃ the reaction 24 hours, to the phenol hydroxyl value less than 50, obtain light yellow resin solution H.Also can add Tetra hydro Phthalic anhydride 35g again and after 120 degrees centigrade of complete reactions, obtain light yellow resin solution H1.
Perhaps in reactor, add the phenol hydroxyl value and be 350 buck resol resin 100g, 2-Butoxyethyl acetate 100g, glycidyl acrylate 62g, triphenyl phosphorus 2.5g, add Resorcinol 1g again, be warming up to 130 ℃ of reactions 20 hours, to the phenol hydroxyl value less than till 45, obtain light yellow resin solution I.Also can add Tetra hydro Phthalic anhydride 10g again and after 90 degrees centigrade of complete reactions, obtain light yellow resin solution I1.
Perhaps in reactor, add the phenol hydroxyl value and be 400 buck resol resin 200g, 2-Butoxyethyl acetate 100g, glycidyl acrylate 60g, triphenyl phosphorus 0.5g, add Resorcinol 0.95g again, be warming up to 110 ℃ of reactions 24 hours, to the phenol hydroxyl value less than till 165, obtain light yellow resin solution J.Also can add Tetra hydro Phthalic anhydride 38g again and after 85 degrees centigrade of complete reactions, obtain light yellow resin solution J1.
Perhaps in reactor, add the phenol hydroxyl value and be 550 buck resol resin 200g, 2-Butoxyethyl acetate 60g, glycidyl acrylate 110g, triphenyl phosphorus 2g, add Resorcinol 0.2g again, be warming up to 120 ℃ of reactions 22 hours, to the phenol hydroxyl value less than till 185, obtain light yellow resin solution K.Also can add Tetra hydro Phthalic anhydride 20g again and after 105 degrees centigrade of complete reactions, obtain light yellow resin solution K1.
Perhaps in reactor, add the phenol hydroxyl value and be 600 buck resol resin 160g, 2-Butoxyethyl acetate 140g, glycidyl acrylate 120g, triphenyl phosphorus 4g, add Resorcinol 0.02g again, be warming up to 125 ℃ of reactions 20 hours, to the phenol hydroxyl value less than till 180, obtain light yellow resin solution K.Also can add Tetra hydro Phthalic anhydride 5g again and after 110 degrees centigrade of complete reactions, obtain light yellow resin solution K1.
Perhaps in reactor, add the phenol hydroxyl value and be 500 buck resol resin 200g, 2-Butoxyethyl acetate 80g, glycidyl acrylate 150g, triphenyl phosphorus 0.05g, add Resorcinol 0.1g again, be warming up to 85 ℃ of reactions 24 hours, to the phenol hydroxyl value less than till 110, obtain light yellow resin solution L.Also can add Tetra hydro Phthalic anhydride 18g again and after 125 degrees centigrade of complete reactions, obtain light yellow resin solution L1.
Prepare welding resistance printing ink then, get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 35g of L1, light trigger 0.5g, thermosetting resin: F48 Resins, epoxy 5g, thinner: DPHA (dipentaerythritol acrylate) 12g, 150# (durene) solvent 42g, filler: talcum powder (less than 2um) 5.5g.Above-mentioned materials is mixed, and high speed dispersion 10 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S1 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 35g of L1, light trigger 1g, thermosetting resin: Dyhard RU 100 5g, F48 Resins, epoxy 44g, thinner: DPHA 8g, ethylene glycol monomethyl ether 2g, filler-silicon dioxide 5g.Above-mentioned materials is mixed, and high speed dispersion 9 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S2 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 35g of L1, light trigger 0.5g, thermosetting resin: 5g, thinner 10g, filler 49g, pigment: phthalocyanine green 0.5g.Above-mentioned materials is mixed, and high speed dispersion 15 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S3 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 75g of L1, light trigger 2.5g, thermosetting resin: 5g, thinner 10g, filler 5g, pigment 2.5g.Above-mentioned materials is mixed, and high speed dispersion 12 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S4 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 40g of L1, light trigger 20g, thermosetting resin: 5g, thinner 10g, filler 10g, pigment 5g, auxiliary agent: defoamer 10g.Above-mentioned materials is mixed, and high speed dispersion 8 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S5 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 60g of L1, light trigger 4g, thermosetting resin: 6g, thinner 15g, filler 13g, pigment 1g, auxiliary agent 1g.Above-mentioned materials is mixed, and high speed dispersion disperses to obtain fineness less than 20 microns welding resistance printing ink S6 with three-roll grinder till evenly.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 40g of L1, light trigger 2g, thermosetting resin: 10g, thinner 11g, filler 6g, pigment 30g, auxiliary agent 1g.Above-mentioned materials is mixed, and high speed dispersion 11 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S7 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 40g of L1, light trigger 2g, thermosetting resin: 8g, thinner 11g, filler 10g, pigment 20g, auxiliary agent 9g.Above-mentioned materials is mixed, and high speed dispersion 14 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S8 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 70g of L1, light trigger 1g, thermosetting resin: 9g, thinner 10g, filler 5g, pigment 3g, auxiliary agent 2g.Above-mentioned materials is mixed, and high speed dispersion 11 minutes disperses to obtain fineness less than 20 microns welding resistance printing ink S9 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 36g of L1, light trigger 1g, thermosetting resin: 6g, thinner 50g, filler 5g, pigment 1g, auxiliary agent 1g.Above-mentioned materials is mixed, and high speed dispersion 10 minutes or till evenly disperses to obtain fineness less than 20 microns welding resistance printing ink S10 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 37g of L1, light trigger 1g, thermosetting resin: 5g, thinner 11g, filler 45g, pigment 0.5g, auxiliary agent 0.5g.Above-mentioned materials is mixed, and high speed dispersion 10 minutes or till evenly disperses to obtain fineness less than 20 microns welding resistance printing ink S11 with three-roll grinder.
Perhaps get the molten resin solution A of above-mentioned synthetic photosensitive bases, B, C, G, G1, H, H1, I, I1, J, J1, K, K1, L or the arbitrary 37g of L1, light trigger 1g, thermosetting resin: 45g, thinner 11g, filler 5g, pigment 0.5g, auxiliary agent 0.5g.Above-mentioned materials is mixed, and high speed dispersion 12 minutes or till evenly disperses to obtain fineness less than 20 microns welding resistance printing ink S12 with three-roll grinder.
Welding resistance printing ink S1-S12 is carried out aforesaid method measure the touch dry of each printing ink (preliminary drying drying property), photosensitivity, development, tack, anti-scolding tin thermal shocking, acid resistance, alkali resistance, flexibility, the result is excellent.
Photosensitizers in the present composition (being light trigger) has no particular limits, and can enumerate commonly used having: anthraquinone classes such as benzophenone, phenylbenzyl ketone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone; 2,4--dimethyl thioxanthone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether etc. and benzoin alkyl ether, 2,2--dimethoxy-2-phenyl methyl phenyl ketone, 2,2--diethoxy-2-phenyl methyl phenyl ketone; 1,1-dichloroacetophenone, 2-methyl isophthalic acid-[4-(methyl thio phenyl (methyl)]-2-morpholinyl acetone, 1,2-benzyl-2-dimethyl amido-1-(4-morpholinyl phenyl)-butane-1-ketone, N, amido acetophenones such as N-dimethyl amine benzoylformaldoxime; The methyl phenyl ketone dimethyl ketal, the light trigger that ketal classes such as benzyl dimethyl ketal etc. are commonly used, but be not limited to above cited light trigger.
Thermoset composition among the present invention contains the resin of two and above epoxy group(ing) in its molecule, do not have other special restriction in addition.Resins, epoxy commonly used can list bisphenol-type epoxy resin, phenol aldehyde type epoxy resin, bisphenol-s epoxy resin, cycloaliphatic epoxy resin, triglycidyl isocyanurate, xenyl Resins, epoxy.Said other solidifying agent is meant that one or more that can make that the ring resin crosslinks maybe can promote compound that it is crosslinked or resin merge and uses, specifically can list: Dyhard RU 100 and modified compound thereof, trimeric cyanamide and modified compound thereof, imidazoles and modified compound thereof, organic amine, guanidines, guanamine resin, thiol compound and aminoresin.
The present invention has no particular limits the photosensitivity monomer of the unsaturated group that contained in the thinner, commonly used lists: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Hydroxyethyl acrylate, the photoactive monomer that contains a unsaturated group in (methyl) vinylformic acid laurel tallow equimolecular, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, trishydroxymethyl three (methyl) acrylate, ethoxyquin trishydroxymethyl three (methyl) acrylate ester, third oxidation trihydroxy methyl three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane three (methyl) acrylate, third oxidation tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc., but be not limited only to this.Then can list as solvent: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, propylene glycol ethers such as two propyl alcohol monobutyl ethers, vinyl acetic monomer, the ester acid butyl ester, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, the 2-ethoxyethanol acetic ester, the diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetic ester, the propylene glycol monobutyl ether acetic ester, dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate ester etc.Ketones solvent has: butanone, and cyclohexanone, isophorone etc., aromatic solvent has: toluene, dimethylbenzene, durene, the oil series solvent has: petroleum naphtha, oxidation petroleum naphtha, solvent naphtha etc., these solvents can separately or merge use more than two kinds.The present invention there is no additional limits to this.
Filler among the present invention has no particular limits, and commonly used enumerates: calcium dioxide, talcum powder, barium sulfate, gas phase hard charcoal orchid, ground barium sulfate, silicon-dioxide, the mineral filler that clay, lime carbonate, aluminum oxide, mica powder, high adjacent soil etc. are commonly used.
Title complex of the present invention, tinting pigment has no particular limits, and commonly used lists: the tinting pigment that phthalocyanine green, pthalocyanine blue, Viola crystallina, titanium dioxide, carbon black etc. are commonly used.
As required, title complex auxiliary agent of the present invention can also cooperate heat polymerization inhibitors, thixotroping tackifier, dispersion agent, flow agent, defoamer etc.
According to the present invention, a kind of printed circuit board can also be provided, on circuit card, scribble liquid photosensitive welding resistant printing ink of the present invention, just constituted a kind of novel welding resistance circuit card.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1, a kind of liquid photosensitive welding resistant printing ink is characterized in that, it comprises photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and auxiliary agent; Wherein, the weight percent of each component is:
The molten resin content of photosensitive bases is 35～75%,
Photoinitiator levels is 0.5～20%,
Thermosetting resin content is 5～49%,
Amount of diluent is 10～54%,
Filler content is 5～49%,
Pigment content is 0～30%,
Auxiliary agent content is 0～10%;
Wherein, described photosensitivity alkali soluble resin is made by following method: adding the phenol hydroxyl value in reactor is the buck resol resin of 300-600, unsaturated thiazolinyl acid glycidyl ester, solvent, catalyzer, stopper, be heated to 85-130 degree centigrade react to the phenol hydroxyl value stable till; Wherein,
The epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and the phenolic hydroxyl group mole ratio of described resol are 0.2-0.8;
The weight percent of described solvent and described resol is 25% to 150%;
The weight percent of described catalyzer and described resol is 0.01 to 5%;
The weight percent of described stopper and described resol is 0.01 to 1%.
2, liquid photosensitive welding resistant printing ink according to claim 1 is characterized in that,
Described unsaturated thiazolinyl glycidyl ester is glycidyl methacrylate, glycidyl acrylate or both miscellanys;
Described solvent is durene, dimethylbenzene, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol monobutyl ether acetate, dipropylene glycol ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate or its miscellany;
Described catalyzer is triphenyl phosphorus, antimony triphenyl, N, accelerine, N, N-dimethyl benzylamine, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, sodium hydroxide or potassium hydroxide;
Described stopper is Resorcinol, p methoxy phenol, 2,5-dimethyl Resorcinol, 1,4-naphthalenediol or its miscellany.
3, liquid photosensitive welding resistant printing ink according to claim 1 is characterized in that,
The weight percent of described catalyzer and described resol is 0.5-2.5%;
The weight percent of described stopper and described resol is 0.02% to 0.2%.
4, liquid photosensitive welding resistant printing ink according to claim 1 is characterized in that, the photosensitivity alkali soluble resin to making also adds saturated acid anhydrides or unsaturated acid anhydride, be heated to 85-130 degree centigrade react to acid number stable till; Wherein, the weight percent of saturated acid anhydrides or unsaturated acid anhydride and described resol is below 40%.
5, liquid photosensitive welding resistant printing ink according to claim 4 is characterized in that, described saturated acid anhydrides or unsaturated acid anhydride are Tetra hydro Phthalic anhydrides, MALEIC ANHYDRIDE, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
6, according to the arbitrary described liquid photosensitive welding resistant printing ink of claim 1 to 5, it is characterized in that the product that the hybrid reaction that described buck resol resin is A and B obtains;
Wherein, A is formaldehyde, phenyl aldehyde or both miscellanys, and B is phenol, sylvan or both miscellanys;
And described buck resol resin has following constitutional features:
R wherein
1Be C
6H
5Or H, R
2Be H or CH
3
7, according to the arbitrary described liquid photosensitive welding resistant printing ink of claim 1 to 5, it is characterized in that the weight percent of each component is:
The molten resin content of photosensitive bases is 35～60%,
Photoinitiator levels is 0.5～15%,
Thermosetting resin content is 5～20%,
Amount of diluent is 15～45%,
Filler content is 10～49%,
Pigment content is 0～15%,
Auxiliary agent content is 0～5%.
8, a kind of liquid photosensitive welding resistant printing ink is characterized in that in the application of printing circuit board, in printing circuit board, adopts liquid photosensitive welding resistant printing ink as solder resist; Wherein, described liquid photosensitive welding resistant printing ink comprises photosensitivity alkali soluble resin, light trigger, thermosetting resin, thinner, filler, pigment and auxiliary agent; Wherein, the weight percent of each component is:
The molten resin content of photosensitive bases is 35～75%,
Photoinitiator levels is 0.5～20%,
Thermosetting resin content is 5～49%,
Amount of diluent is 10～54%,
Filler content is 5～49%,
Pigment content is 0～30%,
Auxiliary agent content is 0～10%;
Wherein, described photosensitivity alkali soluble resin is made by following method: adding the phenol hydroxyl value in reactor is the buck resol resin of 300-600, unsaturated thiazolinyl acid glycidyl ester, solvent, catalyzer, stopper, be heated to 85-130 degree centigrade react to the phenol hydroxyl value stable till;
Wherein, the phenolic hydroxyl group mole ratio of the epoxy mole number of described unsaturated thiazolinyl acid glycidyl ester and described resol is 0.2-0.8; The weight percent of described solvent and described resol is 25% to 150%; The weight percent of described catalyzer and described resol is 0.01 to 5%; The weight percent of described stopper and described resol is 0.01 to 1%;
And described buck resol resin is the mixture of A and B; Wherein, A is formaldehyde, phenyl aldehyde or both miscellanys, and B is phenol, sylvan or both miscellanys;
And described buck resol resin has following constitutional features:
R wherein
1Be C
6H
5Or H, R
2Be H or CH
3
9, liquid photosensitive welding resistant printing ink according to claim 8 is characterized in that in the application of printing circuit board,
Described unsaturated thiazolinyl glycidyl ester is glycidyl methacrylate, glycidyl acrylate or both miscellanys;
Described solvent is durene, dimethylbenzene, ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol monobutyl ether acetate, dipropylene glycol ethyl ether acetate ester, dipropylene glycol monobutyl ether acetate or its miscellany;
Described catalyzer is triphenyl phosphorus, antimony triphenyl, N, accelerine, N, N-dimethyl benzylamine, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, sodium hydroxide or potassium hydroxide;
Described stopper is Resorcinol, p methoxy phenol, 2,5-dimethyl Resorcinol, 1,4-naphthalenediol or its miscellany.
10, liquid photosensitive welding resistant printing ink according to claim 8 is characterized in that in the application of printing circuit board, and the weight percent of each component is:
The molten resin content of photosensitive bases is 35～60%,
Photoinitiator levels is 0.5～15%,
Thermosetting resin content is 5～20%,
Amount of diluent is 15～45%,
Filler content is 10～49%,
Pigment content is 0～15%,
Auxiliary agent content is 0～5%.
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| JP5623886B2 (en) * | 2009-12-09 | 2014-11-12 | 富士フイルム株式会社 | Colored photosensitive composition, method for producing color filter, color filter, and liquid crystal display device |
| CN102548232B (en) * | 2011-11-16 | 2014-05-21 | 大连崇达电路有限公司 | Method for preventing circuit board solder mask ink from blocking hole |
| CN104808436B (en) * | 2014-01-27 | 2017-11-24 | 太阳油墨（苏州）有限公司 | Alkali development-type photosensitive resin composition, dry film and solidfied material and printed circuit board (PCB) |
| JP6497639B2 (en) * | 2014-03-04 | 2019-04-10 | アイカ工業株式会社 | Thermosetting resin composition, cured product and method for producing modified phenolic resin |
| CN104974594B (en) * | 2015-07-13 | 2016-08-31 | 深圳市容大感光科技股份有限公司 | The ink composite of a kind of water-soluble solvent, its application and printed circuit board (PCB) |
| CN106243827B (en) * | 2016-09-28 | 2017-06-16 | 南雄市科鼎化工有限公司 | A kind of thermosetting ink of the anti-chemical nickel and gold of selectivity |
| CN108129623A (en) * | 2018-01-03 | 2018-06-08 | 苏州市明大高分子科技材料有限公司 | Cashew nut oil modified phenolic aldehyde acrylic resin, preparation method and application |
| CN108753037A (en) * | 2018-05-25 | 2018-11-06 | 邹峰 | A kind of preparation method of compound resin base solder mask |
| CN112285128A (en) * | 2020-11-27 | 2021-01-29 | 东莞市科佳电路有限公司 | Method for detecting copper leakage of printing ink |
| CN112928034A (en) * | 2021-01-27 | 2021-06-08 | 中南大学 | Method for manufacturing controllable cavity in power electronic solder layer |
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