TW474964B - Water-soluble photosensitive composition - Google Patents

Abstract

The invention discloses a water-soluble photosensitive composition which is used in paint, printing ink, or as the photosensitive material of printed circuit board. The composition is especially suitable to be used as solder resist. The composition includes (a) 5 to 50 wt% latex, which is obtained by emulsifying an unsaturated double bond-containing monomer with a polymeric reactive emulsifier and then polymerized, wherein the polymeric reactive emulsifier contains both carboxy group and unsaturated double bond; (b)5 to 50 wt% unsaturated double bond-containing reactive diluent, which is emulsified in the emulsifier of (a); (c) 0.1 to 15 wt% photoinitiator; and (d) 0.5 to 30 wt% thermosetting resin.

Description

2. Description of the invention (1) The present invention relates to a decontamination system containing an emulsified polyphotographic tree containing 4 daggers, which has potential problems. Therefore, in the current forming process, the solvent still escapes in the product, so it does not contain organic water-based resin. That is to address the shortcomings of Japanese proprietary solvents, disasters, etc. U.S. special water> Valley fluid, but under reduced pressure to dissolve and increase the production of the acrylic base in the United States, emulsified polysulfate) ^ The five series are related to the organic solubility of the lipid composition, which has been changed from alkali to There is a lot of organic, and the influence of solvents that contain more than the above will be contaminated. The solvent must be dissolved, and the solvent must be synthesized. Lithion 5, the copolymer is a kind of water-based photosensitive resin composition, especially a photosensitive resin composition of latex having a polymer-reactive latex having a retardation group and an unsaturated double bond. It has been used in photoresist and green paint for decades. The solvent is used, but it is replaced by the aqueous developer because of environmental protection and recycling costs caused by the volatilization of the human body during the operation. However, because of the resin content of the organic solvent as the solvent, the photosensitive resin group solvent, when coating and drying operations, the health and working environment of these organic workers. Therefore, the water-soluble photosensitive resin composition has its needs, but there is a concern that the mono-water-based composition is poor in electrical insulation. This problem is improved. This problem can be overcome only when the solvent used in Case No. 9-1 8 5 1 6 7 is environmental pollution, which affects the safety of labor operations, and easily causes the media to be changed to water. In Nos. 4 6 8 and 7 8, although the resin composition can be prepared into a process, a large amount of solvent must be used. After the synthesis is completed, it is dissolved in water. This process requires a large amount of energy. 0 4 5, 4 3 5 In the process, it is firstly emulsified and polymerized to contain a carboxyl group, and then neutralized with a lye to obtain a resin dispersion. The sodium lauryl sodium sulfate is sodium alkyl aryl.

474964 V. Description of the invention (2) * --- sul fonate) is an emulsifier, but it will remain in the composition and affect the electrical insulation properties. Therefore, 'the purpose of the present invention is to solve the above problems, and provide a water, f-light resin composition, which does not contain organic solvents, and can maintain physical properties such as photosensitivity, electrical insulation, heat resistance, hardness, etc. Therefore, it can be used in coatings, inks, or as a photosensitive material for printed circuit boards, especially for green paint. The aqueous photosensitive resin composition of the present invention comprises the following components: (a) 5 to 50 weight percent of latex, the latex is emulsified with a polymer containing an unsaturated double bond using a polymer reactive agent, and then polymerized It is obtained by reaction synthesis. The surface molecule reactive emulsifier contains both carboxyl group and unsaturated 2 double bonds, (b) 5 to 50 weight percent of reactive diluent with unsaturated double bonds, which is emulsified in ingredients ( a) an emulsifier; (c) a photoinitiator at a weight ratio of 5 to 100%; and (d) a thermosetting resin at 0.5 to 30% by weight. The preferred content of each component of the composition of the present invention is: ~ U weight percent of latex; (b) 10 to 45 weight percent of a reactive diluent; (c) 1 to 10 weight percent of a light initiator; and (d) ) 2 to 20 thermosetting resin. In order to further explain the content of the present invention, each component of the water-based photosensitive tree moon composition is described one by one below. According to the present invention, the latex of the component u) is emulsified with a polymer-reactive chemical emulsifier-single fluorene containing unsaturated double bonds, and then synthesized through polymerization reaction. Among them, the polymer-reactive emulsifier contains both Unsaturated double bond, which is composed of carboxyl group-containing polymer and acrylic monomer with epoxy group

474964 V. Description of the invention (3) Resulting from the reaction, this polymer containing a retarder can be, for example, styrene / acrylic acid copolymer (styrene / acrylic acid copolymer); and this acrylic monomer with epoxy groups It can be uiycidy1 methacrylate (GMA), glycidyl me acr me acrylate, glycidylmethyl acrylate, methacrylic acid methacrylate glycidylmethyl-thacrylate), 4-epoxybenzyl rylate and 4-ep0Xy benZyl thacry late, etc. The reaction between the carboxyl polymer and the acrylic monomer containing an epoxy group can be performed in the presence of a catalyst and a double bond reaction inhibitor at 50 to 120 ° C. Taking Glycidyl Acrylate (GMA) as an epoxy-containing acrylic monomer as an example, the polymer reaction and the emulsification of the present invention can be obtained from the following reactions ^

Page 7 474964

〇 + h2c.ch—ch2—〇_c a c ~ wide mouth \ / i 0 CH3

COOH C〇〇H

GMA short polymer C = 〇 COOH 0 ch2

HO-CH? H2 0 c = 〇 Bu H3 ch2

Polymer Reactive Emulsifier Qi The characteristics of the polymer reactive emulsifier of the present invention are as shown above. It has both Weiji and unsaturated double bonds. When the monomer-reactive emulsifier of the present invention emulsifies a monomer, it can also participate in the polymerization reaction of the monomer through a double bond, so it can provide a more stable structure. The polymer reactive emulsifier of the present invention has an acid value of 30 to 300 mg-KOH / g, preferably 100 to 200 mg-KOH / g; its molecular weight (Mw) is 200 to 100,000 Between, preferably between 5,000 and 30,000. In the present invention, the unsaturated double bond-containing monomer used in the component (a) may be acrylic, aromatic vinyl, chloroprene, ethylene gas, ethyl acetate, or a mixture thereof. The acrylic monomers may be acrylic acids,

Page 8 474964

Acrylic vinegars, methacrylics, and methacrylates. Specific examples include methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, and methyl methacrylate (n ^ thyi methacrylate), ethyl methacrylate, butyl methacrylate, and ethylhexyl acrylate. The aromatic vinyl monomer may be, for example, ethylene. According to the present invention, the above-mentioned polymer-reactive emulsifier is used to emulsify an unsaturated double bond-containing monomer, and the component (a) 1 latex obtained through polymerization reaction has a molecular weight (Mw) of 5, 0 0 0 The molecular weight is between 10,000 and 100,000, preferably between 10,000 and 500,000. In the present invention, the component (b) is a reactive diluent having an unsaturated double bond, and is emulsified by the polymer-reactive emulsifier described in the component (a). In order to improve the insulation, the reactive diluent is preferably a lipophilic one, and more preferably a monomer having excellent insulation. Appropriate reactive diluents such as acrylic monomers, more preferably acrylic monomers with more than two unsaturated double bonds, specific examples include 1,4-butanediol di (meth) acrylate (1,4-butanediol di (meth) acrylate), 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Group) neoopentylglycol di (meth) acry late, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Diopentylglycol adipate di (meth) acrylate, neoopentylglycol di (meth) propionate, neopentylglycol di (met h) acry 1 ate

474964 V. Description of the invention (6) hydroxypi va late), dicyclopentadienyl di (meth) acry1 ate), caprolacton, modified di (fluorenyl) Dicyclopentadienyl acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate , Trimethylol propane tri (meth) acrylate, dipentaerythritol tri (meth) acry1 ate, propionate Quality pentamexyl bis (meth) acrylic acid vinegar, pentaerythritol tri (meth) acrylic acid ester, propylene oxide modified trimethylol tris (meth) acrylic acid Propyl ester, tris (acryloxyethyl) isocyanurate, propionic acid modified dipenterythritol penta (methyl) propionate, dipenterythritol hexa ( Meth) acrylic acid or mixtures thereof. According to the present invention, the photoinitiator used in component (c) is preferably one that can generate free radicals upon light irradiation, and can be used singly or in combination of a plurality of photoinitiators. Suitable photoinitiators may be benzoin, benzoin alkyl ether, benzil, ketals, acetophenones ), Benzophenone (b enz ophenone), 4, 4, -dimethyl-amino-benzophenone (4, 4,-dimethyl-amino-benzophenone), thioxanthone 4 Or thioxanthones

Page 10 474964 V. Description of the invention (7) ^^ (morpholino-propanones), etc. According to the present invention, the thermosetting resin of the component (d) may be epoxy resin, and the appropriate epoxy resin may be bisphenol A epoxy resin (bisphenol / epoxy resin), bisphenol F epoxy resin, and bisphenol S ring. Oxygen resin, phe η ο 1 novo 1 ac epoxy resin, cresol novolac epoxy resin, brominated epoxy resin, phthalic acid Diglycidyl phthalate resin, triglycidyl isocyanate, tetraglycidyl ether of tetrakis (4-hydroxyphenyl) ethane ), Rubber modified epoxy resin (rubber modified epoxy resin), Shi Xi _ modified epoxy resin (silicone modified epoxy resin) or ε-caprolactone modified epoxy resin (ε-caprolactone modified epoxy resin ) ° The preferred epoxy resin is one having more than two epoxy groups in one molecule. ¥ When it is cross-linked with the thermosetting group in the aqueous photosensitive resin composition of the present invention, the composition can no longer contain hydrophilic of Group, the insulating lift. In addition, the water-based photosensitive resin composition of the present invention may be supplemented with a filler, such as silicon dioxide, barium sulfate, or talc (ta 1 c), as necessary. The filler is preferably added in an amount of less than 40% by weight of the total composition. In addition, the water-based photosensitive resin composition of the present invention may be added with a small amount of additives, such as a colorant, a defoaming agent or a flattening agent, as necessary. The water-based photosensitive resin composition of the present invention has the following advantages: (1) The latex is synthesized in the water phase, and there is no need for a process of solvent exchange, so it can save

Page 11 474964 V. Description of the invention (8)-*-A large amount of energy; (2) Polymer reactive emulsifiers contain unsaturated bonds, which can form cross-links with the polymers inside the latex, which will not be caused by migration. Decrease physical properties; / (3) Because the polymer-reactive emulsifier contains a carboxyl group, it can neutralize with ammonia water to form a hydrophilic group, and can react with a thermosetting resin during thermal curing, so it will not affect its electrical properties. In order to make the above and other objects, features, and advantages of the present invention more obvious If ', the preferred embodiments are specifically described below, and described in detail below. Preparation Example 1: Synthesis of Polymer Reactive Emulsifier (A) 200 grams of stupid ethylene / acrylic acid copolymer (j — 69〇; J〇hns〇n Co .: made by the company, acid value = 24 0 mg-KOH / g) and 200 g of methoxyethanol at 8 (TC; dissolve with stirring; 0.2 g of hydroquinone monomethyl ether) was added as a double bond reaction inhibitor, and 1.6 G of triphenyl phosphine was used as a catalyst, and it was stirred and dissolved at 8 (TC; 24 g of glycidyl propylene acrylate (GMA) was finally added and reacted at 80 ° C for 5 hours; finally, water, precipitation, filtration and Drying to obtain the required polymer-reactive emulsifier (A), the molecular weight (Mw) is 17,000, the acid value is 170 mg-KOH / g. Preparation Example 2: Polymer-reactive emulsifier Synthesis of Agent (B) 200 grams of styrene / acrylic acid copolymer (J-690) and 200 grams of methoxyethanol were stirred and dissolved at 80 ° C; 0.2 grams of hydroquinone monomethyl was added Ether and 1.6 grams of triphenylphosphine, dissolved at 80 ° C with stirring; finally added

Page 12 474964 V. Description of the invention (9) 48 g of propyl methacrylate (GMA), at 80. 〇React for 8 hours; finally add water, precipitation, filtration and drying to obtain the required polymer reactive emulsifier (β) '. Its molecular weight (M w) is 19,000 and the acid value is 120. mg-KOH / g. Preparation Example 3: Synthesis of Latex (A) 5 g of the polymer-reactive emulsifier (A) of Preparation Example 1, 1.5 g of ammonia water (28%) and 30 g of deionized water were mixed thoroughly, and then added g of A Methyl methacrylate (MMA), emulsified by rapid stirring at 70 ° C. After dissolving 0.15 grams of ammonium peroxodisulfate (amm ο niumperoxydisu 1 fate) in a small amount of water, it was added to the above stirring solution and reacted at 80 ° C for 3 hours to obtain the present invention. Latex (A) in ingredient (a). Preparation Example 4: Synthesis of Latex (B) 5 g of the polymer-reactive emulsifier (A) of Preparation Example 1, 1.5 g of ammonia (28%) and 30 g of deionized water were mixed thoroughly, and then 5 g of Methyl methacrylate and 5 grams of styrene, stir rapidly at 70 ° C. In addition, 0.15 g of ammonium peroxodisulfate was dissolved in a small amount of water, and then added to the above-mentioned stirring solution, and reacted at 80 ° C for 3 hours to obtain the latex (B) in the component (a) of the present invention. Comparative Preparation Example 1: Synthesis of Latex (C) 0.35 g of sodium lauryl sulfate

Page 13 474964 V. Description of the invention (ίο) After the emulsifier is thoroughly mixed with 175 grams of deionized water, 75 grams of methyl methacrylate is added, and the mixture is stirred rapidly at 70 ° C. In addition, 0.5 g of ammonium persulfate was dissolved in a small amount of water, and then added to the above stirring solution, and reacted at 80 ° C for 3 hours to obtain the latex (C) for the comparative example. Examples 1-3: The water-based photosensitive resin composition was prepared in the amounts and chemicals shown in Table 1. The reactive monomer in component (b) was first emulsified with a polymer-reactive emulsifier, and then the component (a ), Latex, light starter of component (c), thermosetting resin of component (d), and other additives, mix and stir well, grind and disperse in a three-roller mill at room temperature. This photosensitive composition was coated on a copper foil substrate, and pre-baked at 80 ° C for 30 minutes. After the substrate is cooled, cover the negative and expose with a UV exposure machine, and then develop with a 1.0% sodium carbonate aqueous solution to test its photosensitivity. Then, it was washed with water and baked at 150 t for 30 minutes to heat harden 'and test its physical properties such as hardness, electrical insulation and heat resistance. The test results are also shown in Table 1. Comparative Example 1-3: The water-based photosensitive resin composition was prepared according to the amounts and chemicals shown in Table 1, and the photosensitive resin composition of the car master example was prepared according to the steps in Example 3, except for Comparative Example 2 and Comparative Example 3. Among the (b) reactive monomers, the test results without polymer reaction (photosensitivity, hardness, and electrical insulation are shown in Table 1. Emulsifiers with emulsifiers and heat resistance of various properties) are also listed.

Page 14 474964 V. Description of the invention (11) Table 1 ·

Example of water-based opaque resin extreme product 1 2 3 1 2 3 Ingredient (a) Latex tA) 50 50--90 90 Latex ⑻--50---Milk knee (C)---50--Ingredient ⑹ Ingredients ⑹ SR-2 class c----14-SR-454RI 20 7 7 20--SR-399P1-13 13--14 Polymer reactive emulsification (A) [4]-Steal 50---High Molecular reactive emulsified (B) W 50 50 > 50--Irgacure 907 (manufactured by Ciba) 1.5 1.5 1.5 1.5 1.5 1.5 Ingredient ⑹ TGIC (epoxy propylene isocyanate) 4.5 4.5 4.5 4.5 4.5 4.5錤 7 7 7 7 7 7 Silicon dioxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Color Kouhua Cyan 0.45 0.45 0.45 0.45 0.45 0.45 Test result Exposure (mJ / crrf) 480 510 500 Delamination cannot be uniformed; & gray scale (21 addiction) 5 9 9 (mils) 5 4 5 6 pencil hardness 6H 6H 6H 6H electrical insulation 1 b | igiS im solder joint heat resistance (260BC, 3 (3 Seconds) itiS it [l] .SR-268: ca tetraethyl ene glycol di acrylate Sartomer's $ 1 hydrophilic anti-corrosive bump · Note [2] .SR-4: 54: Ethoxylated 丙 ¥ propylpropane diene ball. * § (ethoxyUted tfimethylolpropane triaLcrylate) · Sartomer's lipophilic reaction bump for $ 1. Note [3] .SR-399: Dipentamidine Qiu Bingxian (dipentaerythfitol pentaacirylate) · Sartomer's lipophilic reaction Tsui bump · Note [4] · 20 wt% gas water falling liquid 1 with S Μ becomes a polymer reactive emulsification Xie / water / gas water ( 28%) = 10/40/5-Note "51. The surface electrical address is greater than 1x1012Ω. It is considered to be insulating. · As can be seen from Examples 1 to 3 in Table 1, the aqueous photosensitive resin composition of the present invention has good heat resistance. , Developability, resolution, electrical insulation, and high hardness; in contrast, Comparative Example 1 did not add the latex of the present invention (ingredients

Page 15 474964 V. Description of the invention (12) (a)) 'Instead of emulsified latex (C) emulsified with sodiuin lauryl sulfate, the compatibility is too poor and the formula will delaminate. ; In contrast, although the hydrophilic reactive diluent SR_2 68 in Example 2 is soluble in the water-soluble photosensitive tree, the composition does not need to add the polymer reactive emulsification of the present invention, but its insulating properties have failed. As for comparison, In Example 3, the lipophilicity = should = the release agent SR-399 is not based on the polymer inverse of the present invention ^ etiquette, nor can it be modulated into a homogeneous lipid-stabilizing composition. Its excellent performance is suitable for TR water-based circuit boards, and is especially suitable for green paint. : 1 In the case of "printing with ink and printing, the use of water in the present invention with π and τ to maintain excellent physical properties of the use of less organic solvents can greatly reduce the composition of humans and d." Benefits, Jiankang, industrial safety, production cost Although the present invention has a better practical limit = the present invention, anyone familiar with this technique drum. The disclosure is as above, but it is not intended to be used within the scope, and various changes and non-departures Within the spirit of the present invention, therefore, the patent protection of the present invention falls within the scope defined by the scope of the present invention.

Claims (1)

i · A water-based photosensitive resin composition comprising: _ (a) 5 to 50 weight percent of latex, the latex uses a homogeneous emulsifier to emulsify an unsaturated double bond-containing monomer, and is synthesized by ^; σJiuyingnan 丨 5 ~ 50% by weight of reactive dilution with unsaturated double bond d, /, is a polymer-reactive emulsifier released in component (a) (c) 0 · 1 ~ 1 5% by weight of a photoinitiator; and (d) 0.53% by weight of a thermosetting resin, wherein the polymer-reactive emulsifier of this component contains unsaturated double bond n polymer-reactive emulsifier Acid value group between 30 mg-KOH / g, molecular weight between 2000 and 100 () 00 to 2 packages: the composition of the water-based photosensitive tree described in the scope of the application for patent! (a) 20 to 45 weight percent of latex; 10 to 45 weight percent of reactive diluent;: ~ weight percent of light initiator; and (d) 2 to 20 weight percent A hundred knife ratio of thermosetting resin. Object 3. As described in item No. 1 of the Shengu patent scope, the component h + in the bean is composed of A A nine-month-old monomer consisting of the 3 unsaturated double bond A, a voli monomer, and an aromatic vinyl-based ^ f bond. The early body was chosen to be free. ', The body and its mixture of groups 4 · For example, the patent application of the 笳 Flute Q object, in which the acrylic monomer is self-reported ★ water-based photosensitive resin composition methacrylic acid and methyl acrylic resin, acrylic acid In the group consisting of esters and T-propionic acid. Page 18, 474964, Case No. 89100980, June 1, Scope of Patent Application > 5. The water-based photosensitive resin composition according to item 4 of the scope of patent application, wherein the acrylic monomer is methyl free acrylate (Methyl acrylate), ethyl acrylate, butyl acrylate, esters, methyl methacryiate, ethyl methacrylate, butyl methacrylate, and ethylhexyl methacrylate in. 6. The water-based photosensitive resin composition according to item 3 of the scope of patent application, wherein the aromatic vinyl-based monomer is phenethylhydrazone. 7. The water-based photosensitive resin composition according to item 丨 in the scope of the patent application, wherein 40% of the fluorene molecular reactive emulsifier in (a) is composed of a polymer containing a Wei group and a polymer having an epoxy group. Acrylic monomer reaction. 8 · The water-based photosensitive resin composition according to item 7 in the scope of the patent application, wherein the carboxyl group-containing polymer is styrene / acry1ic acid copolymer 〇9 · As in the scope of patent application No. 7 The aqueous photosensitive resin composition described in the above item, wherein the acrylic monomer having an epoxy group is selective glycidyl methacrylate (GMA), glycidyl acrylate, Glycidylmethyl acrylate, glycidylmethyl methacrylate, 4-epoxybenzyl acrylate, and 4-methacrylic epoxy Group (4-epoxybenzyl methacrylate). 1 0. The water-based photosensitive resin composition according to item 1 of the scope of the patent application, wherein the molecular weight of the latex of the component (a) is from 5,000 to J, 0.000, 〇 〇 〇 〇 Page 19 474964 _ Case 1 Tiger 89100980% year | p month day Amendment 6. Between patent application scope. 11. The water-based photosensitive resin composition according to item 1 of the scope of the patent application, wherein the reactive diluent having unsaturated double bonds of component (b) is an acrylic single having two or more unsaturated double bonds. body. 1 2 · The water-based photosensitive resin composition as described in item 11 of the scope of patent application, wherein the acrylic monomer having two or more unsaturated double bonds is selected from neopentyl ethylene glycol di (methyl ) Neopentylglycol di (meth) acrylate, neoopentylglycol adipate di (meth) acrylate, Neopentyl glycol di (meth) acrylate hydroxypivalate, diopentylglycol di (meth) acrylate hydroxypivalate, dicyclopentadienyl di (meth) acrylate, allyl Allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, ethoxylated Ethoxylated trimethylolpropane triacrylate, trimethylolpropane tr i (meth) acry late, dipentyl erythritol tri (methyl) propyl Ester (dipentaerythritol tri (meth) acrylate), penterythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipenterythritol In the group consisting of penta (meth) acrylic acid, dipenterythritol hexa (meth) acrylic acid S, and the mixture mentioned above. 1 3. Composition of water-based photosensitive resin as described in item 1 of the scope of patent application Page 20 474964-_____ year γ March 11 _ amendments __ VI. Patent Application Scope The photoinitiator in which the wound (c) is formed is a free radical that can be generated by light irradiation. 1 4 · The water-based photosensitive resin composition as described in item 3 of the patent application range, wherein the photoinitiator is benzoin, benzoin alkyl ether , Benzi aldehyde (benzi 1), ketals, acetophenones, benzophenone, 4,4'-dimethyl-amino-dibenzoyl (4,4-dimethyl-amino-benzophenone), thioxanthones and morpholino-propanones. 15. The thermosetting resin of the component (d) in the water-based photosensitive resin composition ′ described in item 1 of the scope of patent application is an epoxy resin having two or more epoxy groups in one molecule. 1 6 · The water-based photosensitive resin composition described in item 5 of the patent application 'wherein the epoxy resin is bisphe η 1 A epoxy resin, bisphenol F epoxy Resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol nov〇lac ep〇xy resirl, desertified epoxy resin (Bromina ted epoxy resin), diglycidyl phthalate resin, and triglycidyl isocyanate. 1 7. The water-based photosensitive resin composition according to item 1 of the patent application scope, further comprising a filler. No. 474964 Case No. 89100980 Amendment VI. Application scope 1 8. The water-based photosensitive resin composition described in item 1 of the scope of patent application, which further includes an additive. 19. The water-based photosensitive resin composition according to item 1 of the scope of patent application, which is used as a green paint. Page 22