TW475097B - A negative photoactive composition - Google Patents

Abstract

The present invention discloses a photoactive composition useful in manufacturing printed circuit board. The composition consists of (a) a binder, (b) a photo initiator, and (c) unsaturated photo monomer. The binder is obtained by the reaction of the following reactants: (I) a styrene-maleic anhydride resin containing repetitive styrene and anhydride group monomer, (ii) an unsaturated compound containing at least a hydroxyl group and at least three acrylic functional groups, and (iii) a saturated alcohol. The styrene-maleic anhydride resin is a polymerization product of styrene and maleic anhydride with a repetition ratio between 3:1 to 1:1 and a molecular weight range preferably between 800 and 100000. The photoactive composition is characterized by high photosensitivity, high hardness, good chemical resistance, no low molecular weight irritating substance and increased degree of crosslinking after being exposed to light.

Description

475097 V. Description of the invention (1) Scope of the invention The present invention relates to a novel negative photosensitive composition, which is used as a photoresist and solder resist for etching in the manufacturing process of printed circuit boards. More specifically, the photosensitive composition has high sensitivity, high chemical resistance, and high hardness, and is an alkaline water developing type. A more important advancement of the present invention is that the photosensitive composition does not contain molecules that cause harm to health and the environment. In the manufacturing process of printed circuit boards, the photosensitive composition plays an important role: two materials, such as photoresist and solder resist, are used for engraving. The former is used for engraving of copper conductor lines. The surface is peeled off; the latter is used to coat copper wires after the production of copper wires is completed. In the process of dip soldering, it is possible to avoid connecting the conductors to achieve the effect of insulation. The two materials mentioned above can be applied in liquid or dry film state. The liquid photosensitive materials are usually screen printing, roll coating (r 0 1 1 erc 〇ating), curtain coating (curtain coating) and dipping. A method such as dipcoating is applied to the substrate of the circuit board. The dry film photosensitive material is coated with a liquid photosensitive material on a transparent substrate in advance, and the photosensitive sound is attached to the substrate of the circuit board by hot pressing during use. ^ According to the development technology, the photo-sensitive materials can be divided into two types of development: solvent development and inspection. The former uses solvents (usually organic solvents and R water to remove the exposed part of photoresist (for negative photoresist In terms of operation, there are pollution caused by solvent volatilization and waste liquid recovery, which leads to lower cost. The point has been gradually replaced by the latter; if ^ 1 in the photosensitive composition lacks a carboxyl group, etc. Use alkaline water to dissolve the knife containing &

475097 V. Description of the invention (2) The solution is used as a developing solution, because during the development of alkaline water, the carboxyl group will neutralize with sodium carbonate to form salts, and emulsify the photosensitive composition of the unexposed part and disperse it in water to reach Development function. · Knife The sensitivity of the photosensitive composition is related to the degree of crosslinking after exposure. Generally, the more unsaturated double bonds the compound has, the higher the degree of cross-linking. However, if an excessive amount of photomonomer is added, the photosensitive layer is likely to be too sticky, which is disadvantageous for the operation of the image transfer process. When the photosensitive material in the dry film type is used, the photosensitive layer is protected by a polyester film (polliner f ilm), which does not cause problems such as contamination of the exposed negative film and oxygen inhibition of the polymerization reaction. Cross-linking monomers are provided, because of &, the preparation of water-developable dry film, the only thing to do is to use the polymer for film formation (binde " side material ::: soil &: additional unsaturated double However, the liquid photosensitive material should use Nissho's "None?" Film protection. The dried coating film before exposure is hard: visible; seek; don't matter. "Therefore, you can't add" excessive sensitivity, " Must have a high score in film-forming ί Reveal the feeling: sex: adult Π σ :::: as in US art 50 5 53 78 is not equal to the number of groups containing == \ points into ^ by epoxy resin In this way, β-photometry can be induced in the film-forming polymer by introducing σ into the lamp reaction. However, as disclosed in the Xuan patent: and double bonds to increase the sensitivity of the base, it is a solvent-developed photosensitivity. Property: $ molecule does not contain carboxy shadow type. In order to achieve alkaline water development 2, 'and become 4 not' instead of alkaline water Zhao 6 1 -24386 9 and Pingbu 22: Such as the film-forming / non-composing composition disclosed in the US-specialized art 5…, and the film-formed / non-exposed composition disclosed in the US-specialized art 5 0 5 5 3 78 Reaction to guide

475097 V. Description of the invention (3) Yanba; ’In addition to achieving the purpose of alkaline water development, the unsaturated double bond introduced by the film-forming door knife also improves the photosensitivity. Although the sexual composition has high sensitivity and excellent alkaline water ^ = the use of excessive "two two dimers (such as acrylic acid or fluorenyl acrylic acid) in the sub-reaction process, these unsaturated compounding two materials: Volatile and highly toxic low-molecular-weight compounds' make the final photosensitive injection molding and finished products, due to these excessive low-molecular compounds, right-exciting and harmful to the human body, which is the main disadvantage of the above system. In addition to oxygen resin modified synthetic film-forming polymers, liquid photosensitive materials are also modified with styrene-maleic anhydnde resin (SMA resin). For example, the United States 4 7 6445 2, Among the compositions disclosed in US Patent 5 3 6 4 7 3 6 and Japanese Patent Publication No. 4-23 9 0007, 'the partially esterified SM A resin is used as the film-forming polymer U /, Manufacture of photosensitive composition. In the above system, SMA resin is a low-molecular saturated alcohol that undergoes a ring-opening reaction, and a carboxyl group is introduced into the side chain. Since the film-forming polymer 6 has a carboxyl group, the photosensitive composition is formulated. It is alkali-soluble and has no carboxyl group because it is not used Low-molecular unsaturated compounds, the finished product is non-irritating to the human body. However, because the film-forming polymer produced does not contain unsaturated double bonds, the coating film is hardened due to insufficient cross-linking degree, and is resistant to practical applications. Poor chemical properties and hardness. In order to increase the degree of cross-linking of the styrene-marine anhydride resin system, as disclosed in the US patents 5 0 8 7 5 5 2, 5 1 1 4 8 3 0 and 5 2 9 6 3 3 4 In the composition, in the ring-opening reaction of the styrene-maleic anhydride resin, a monofunctional functional alcohol and a mono-functional unsaturated alcohol are used, such as (fluorenyl) acrylic acid-2-ylethyl ether. hydroxyethyl

C: \ Program Files \ Patent \ li. Ptd Page 6 475097 5. Inventive Note (4) (ineth) acrylate) In addition to introducing carboxyl groups into the side chains, unsaturated double bonds are also introduced, which can increase the degree of cross-linking. It further improves the chemical resistance and hardness of the coating film. Although the above system improves the performance of the photosensitive material, it also has high volatility and irritation because of the use of low-molecular monofunctional unsaturated alcohols. In practical applications, there are concerns about environmental protection and safety. OBJECTS OF THE INVENTION The main object of the present invention is to propose a photosensitive composition having both high sensitivity, high hardness, high chemical resistance, and no low molecular irritant substance. Another object of the present invention is to provide a negative alkaline water-developing photosensitive composition having an improved degree of crosslinking after exposure. Another object of the present invention is to provide a negative type water-receiving developing type photosensitive composition which can be used in a developer and has an increased degree of crosslinking after exposure. Another object of the present invention is to provide a negative alkaline water-developing photosensitive composition which can be used in a solder resist and has an increased degree of cross-linking after exposure. Detailed description of the present invention In the following, the details of the present invention will be described by means of embodiments of the present invention. The present invention is a photosensitive composition, which is suitable for circuit etching resist or solder resist material in the manufacturing process of printed circuit boards. The photosensitive composition contains the following components: (a) a film-forming polymer made of styrene -Marine anhydride resin is prepared by reacting the following two compounds:

II 111 Μ

C: \ Program Files \ Patent \ li. Ptd Page 7 475097 5. Description of the invention (5) (i) Unknown packages & alcohols containing at least three acrylic functional groups per molecule, and (ii) saturated alcohols And (b) photoinitiators; (c) unsaturated photocrosslinking monomers. The above-mentioned photosensitive composition can be subjected to processes such as coating, drying, exposure, and development to produce an image (p a 11 e r η) of a photosensitive material on a printed circuit board substrate. Styrene-malein anhydride resin is synthesized by copolymerization of styrene and maleic anhydride. Since the resin still contains an anhydride group, it can be ring-opened with alcohols (or Esterification) reaction and introduction of a carboxyl group on the side chain. The anhydride content of styrene-malein anhydride resin can be controlled by the ratio of styrene and malein anhydride, and its repeating unit ratio is usually between 1: 1 and 3.1. The more styrene relative to the weight unit , The higher the hardness of the resin after the modification, but the fewer the substituents. When the repeating unit ratio is 1: 1, the more unsaturated double bonds that can be introduced, the higher the degree of cross-linking and sensitivity; moreover, the more the carboxyl group is introduced, the more the photosensitive layer will develop. However, the more the carboxyl group, the better the resolution or adhesion. The appropriate amount should be combined with other additives of the photosensitive liquid. The molecular weight of the styrene-marine anhydride resin is preferably between 8,000 and 100,000. If the molecular weight is too small (less than 8 0 0), the film formation is poor, and when exposed after drying, it is liable to stick and contaminate the exposed film; if the molecular weight is too large (higher than 1 0 0 0 0 0) 'then There is also the risk of unclean development. Proper styrene

C: \ ProgramFiles \ Patent \ li.ptd Page 8 475097 V. Description of the Invention (6)-The maleic anhydride resin can be selected from SMA 1 0 0 0, SMA 2 0 0 0 and SMA 3 0 0 0 (styrene and The corresponding repeating units of Marlin acid are 1: 1, 2: 1, and 3.1 (products of ATTO). The main function of unsaturated alcohols is to provide film-forming polymers with unsaturated double bonds. Each molecule should contain at least three acrylic functional groups. After reacting with the acid anhydride group, it can be used in Adequate unsaturated double bonds (unsatuirated vinyl groups) are introduced into the side chain to improve the cross-linking degree and sensitivity of the photosensitive composition. Appropriate unsaturated alcohols should be selected from those with low volatility, such as pentaerythr triacrylate (U. triacrylate, PETA) and hydroxy diisopenta pentaacrylate (dipentaerythritol pentaacryUte, DPPA). Among them, DPPA can introduce more double bonds, with higher sensitivity, but the film is softer; ρΕΤΑ has a smaller molecular weight 'after grafting', and the side chain is shorter, which can make the film-forming polymer harder, requiring hardness For higher solder resist materials, pm is the better choice. The ratio of hydroxyl equivalents of the acid anhydride group and unsaturated alcohols in ethylene-marine anhydride resin should be between ΐ ·· 〇 · 〇 05 to; [· η q, ^, Wang υ · 9, more suitable equivalence ratio is I: 0 · 2 to 1: 0.7. Too much unsaturated alcohols tend to cause the phenomenon of coating hardness; too little amount of unsaturated alcohols, This leads to insufficient double bonds and a decrease in sensitivity. The function of saturated alcohols is mainly to participate in the ring-opening reaction and introduce sufficient carboxyl groups into the side chain of the film-forming polymer.-The structure of saturated alcohols is not particularly limited. As long as it does not cause irritation to the human body, it can be selected, for example For example, acetic acid, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, n-butanol, 2-methyl-butanol, isoamyl alcohol, n-hexanol, n-heptanol, n-decanol

475097 V. Description of the invention (7) Alcohols (a 1 ky 1 a 1 c 〇h ο 1) such as fermentation, cyclopentanol and cyclohexanol; and methoxyethanol, ethoxyethanol, butoxy Ether alcohols such as ethanol, carbitol, propylene glycol (monomethyl ether), and dipropylene glycol monomethyl ether. The amount and molecular size of the above-mentioned saturated alcohols will affect the carboxyl content and soft hardness of the film-forming polymer. Generally, the higher the amount of saturated alcohols, the higher the ring-opening ratio of the acid anhydride ', the easier the development of the photosensitive material. The equivalents of the acid anhydride and the saturated alcohols should preferably be between 1: 0.2 and 1: 1.0. The molecular size of the saturated alcohols will affect the interchain distance of the film-forming polymer. Generally, the smaller the saturated alcohols, the harder the coating film. If the coating film is too hard before exposure, it will not be conducive to sensitivity. Therefore, the amount and molecular size of saturated alcohols depend on acid compensation and soft hardness. These two properties are related to other additives. & Commonly used photoinitiators are not particularly limited. If it is used for liquid photosensitive materials, the photoinitiator should choose the one with strong light absorption and decomposition ability, to avoid the problem of reducing the degree of cross-linking of the coating surface due to the inhibition of oxygen. Suitable light initiators ^ ^ from 2,2-dimethoxy-2-diphenylethylene diketone (benzil dimethyl, ketal), 2,4-diethylthiodiphenylbenzene (2, 4-diethyl t hi oxanth one), isopropylthioxanthone, 2-methyl-1 ～ [4 一 (methyl ～ 石 危 代) benzene] -2- (1, 4-oxazepine) -propan-1-one (2-methyl-l- (4- (methylthio) phenyl) -2-morphololinpropanone-1) or benzophenone, etc., Combined with 2-diiiiethylaminoethyl benzoate and p-dimethylamine

C: \ PrograinFiles \ Patent \ li.ptd Page 10 475097 V. Description of the invention (8) Ethyi (p-diinethylamin〇) benzoate or Tetramethyldiamine diphenone (M ich 1 er 'sket ο ne Sensitizers such as) can be used to obtain a photosensitive liquid with good sensitivity. Unsaturated photo-crosslinking monomers can provide double bonds for polymerization reaction when the photosensitive material is exposed to UV light. The more unsaturated double bonds in each molecule, the higher the degree of cross-linking. Unsaturated and photocrosslinking monomers may be selected from the group consisting of trimethylolpropane triacrylate, tripropyl triisopropyl triisopropyl triacrylate, pentaerythritol tetraacrylate, and hydroxybisisopentaacrylate Pentaerythritol, dipentaerythritol hexaacry late, bis-phenol A-type epoxy acrylate SI and urethane acrylate. The unsaturated photocrosslinking monomers mentioned above can be used alone or in combination of two or more. The type and amount of the monomers depend on the hardness of the coating film. The above-mentioned film-forming polymer, photoinitiator, and unsaturated photo-crosslinking monomer can already constitute the main components of a general photosensitive composition. If the above composition is used in a liquid solder resist, the unsaturated double bond cross-linking caused by ultraviolet light alone is not enough. It is necessary to use a thermosetting resin such as epoxy resin and appropriate epoxy resin in the formulation. Contains bisphenol A-type epoxy, such as Araldite 6004 (Ciba products Co.), DER 337 (Dow Chemical Co.), Epon 834 (Shell Chemical Co.), and Epon 1001 (Shell Chemical Co ·); phenolic resin type epoxy resin, for example, ECN 1 2 8 0 and ECN 1299

C: \ Program Files \ Patent \ li. Ptd Page 11 475097 V. Description of the invention (9) (Ciba Products Co.), YDCN 704 (Nanya Plastics Co., Ltd.), etc .; aging aldehyde resin epoxy resin, for example, EPN 1139 (Ciba products Co.), DEN 438 (Dow Chemical Co.), etc .; Brominated bisphenol A-type epoxy resin, such as DER 542 and DER 511 (Dow Chemical Co.) , Araldite 801 1 (Ci ba products Co ·), etc. Others have special structures, such as' tetrafunctional EPON 1031 (Shell Chemical Co.), trifunctional Araldite PT-810 (Ciba products Co.) and bifunctional YX-4000 (Shell Chemical Co.) . Generally, the polyfunctional group has a higher degree of cross-linking than the% oxygen resin of the double B energy group, and the hardness and chemical resistance of the coating film are also better. In addition, epoxy resins that are solid at room temperature can avoid the risk of adhesion and contamination of the film when exposed to light. In order to promote the thermosetting property of epoxy resin, curing agents can be added to the photosensitive composition. The suitable curing agent should be selected from the temperature range of room temperature to baking temperature (about 80 ° C.), so as not to cause the ring. The thermal polymerization of oxyresin, but when it is raised to the post-baking temperature, it can quickly cause the epoxy resin to react. Based on this condition, the appropriate hardener is selected: imidazoles 2M4FZ, 2P4M5FZ, 2PHZ, 2PZ, 2P4MZ , 2PZL (Shikoku Chemical Co.), etc .; cyanguanidine (dicyandiamid), etc. In addition to the above components, other components may be added to the photosensitive composition, including fillers (fi 1 1 ers), solvents, dispersants (dispersi ο η agent), anti-sagging agent, and antifoam. (Def oamer), leveling agent (1 eve 1 ing agent), dye or pigment

C: \ PrograinFiles \ Patent \ li.ptd page 12 475097

475097 V. Description of the invention (11) Synthesis of the binding agent (I): Add 820.0 g of Diethylene glycol monoethyl ether acetate in a four-neck reaction flask, raise the temperature to 105 ° C, and add 1165 .0 g SMA 1 〇〇〇 (ATO product, styrene and maleic anhydride relative repeat unit is 1: 1) slowly add to the reaction flask, continue stirring, after the powder is completely dissolved, add 0.5 g of- Hydroquinine, 8.5 g of N, N-dimethylamino group (N, N-dimethylaminopyridine), and 596.0 g of tripropylene acid were reacted for 6 hours. Add 1 36 · 0 g of ethanol, continue the reaction for 8 hours, and dilute with 202.0 g of Naphtha 150 to obtain the resin solution binder (I). Synthesis of Binding Agent (II): Add 750.0 g of monoethyl ether acetate to a four-neck reaction flask, raise the temperature to 105 ° C, and slowly add 1 16 5 · 0 g of SMA 1 0 0 0 In the reaction flask, continue to stir, and after the powder is completely dissolved, add 0.5 g of hydroquinone, 8.5 g of N, N-diamidinoaminopyridine, and 3 5 7. 0 g of hydroxyisotriacrylate. After 6 hours of reaction with glutaryl ester, 3 0..0 g of cyclohexanol was added, and the reaction was continued for 8 hours. After diluting with 2 3 0 · 0 g N aphtha 1 50, a resin solution was obtained. Binder (II).

C: \ Program Files \ Patent \ li.ptd Page 14 475097 V. Description of the invention (12) Synthesis of the binding agent (III): * Add 1130.0 g of propylene glycol monomethyl ether acetate in a four-neck reaction flask inonoinethy 1 ether acetate), increase the temperature to 105 ° C, and slowly add 1200.0 g of SMA 2000 (the relative repeating unit of styrene and marin anhydride is 2: 1) to the reaction bottle, and continue to stir. After the powder is completely dissolved, 0. 5 g of hydroquinone, 8. 5 g of N, N-diaminoaminopyridine, and 410.0 g of hydroxyisopentyl triacrylate were added. After 6 hours of reaction, 9 2 · 0 g was added. Ethanol was continuously reacted for another 8 hours to obtain a resin solution binder (III). Synthesis of Binding Agent (IV): 700.0 g of monoethyl ether glycol acetate was added to a four-neck reaction flask, the temperature was raised to 105 ° C, and 1 200 0 · 0 g of SMA 2 0 0 0 was slowly added to the reaction flask. In the continuous stirring, after the powder is completely dissolved, 0.5 g of p-benzenediazepine, 8. 5 g of N, N-diamidinoamino group and 5 7 0 · 0 g of pentaacrylate Isopentarate. After reacting for 6 hours, 18.0 g of n-propanol was added, and the reaction was continued for 8 hours. After diluting with 350.0 g of Naphtha 1 50, a resin solution binder was obtained ( IV). Synthesis of Binding Agent (V): Add 650.0 g of monoethylstilbene acetate in a four-neck reaction flask to raise

C: \ Program Files \ Patent \ li. Ptd Page 15 475097 V. Description of the invention (13) When the temperature reaches 105 ° C, add 16.50.0 g of SMA 1 0 0 0 to the reaction bottle slowly. Keep stirring until powder After completely dissolved, 0.5 g of p-benzenedifluoride, 8.5 g of N, N-diamidinoamino group, and 450.0.g of hydroxydiisopentapentapentaacrylate were added. After 6 hours of reaction, add 3 4 0 · 0 g ethylene glycol monobutyl 1 ether (butyl cellosolve), the reaction was continued for 8 hours, and diluted with 400.0 g Naphtha 150 to obtain the resin solution binder (V). Shuyuezhi Synthesis (B indersynthese) (I) (II) (III) (IV) (V) SMA1000 1165.0 1165.0 1165.0 SMA2000 1200.0 120〇 · 0 hydroxyisoamyl triacrylate 596.0 357.0 410.0 hydroxydiisopenta pentaacrylate Ester 570.0 450.0 Ethanol 136.0 92.0 N-propanol 180.0 Cyclohexanol 300.0 Ethylene glycol monobutyl ether 340.0 Hydroquinone 0.5 0.5 • 0.5 0.5 0.5 N, N-dimethylaminopyridine 8.5 8.5 8.5 8.5 8.5 Acetic acid mono Lithyl ether propylene glycol 1130.0 Monoethyl ether acetate 820.0 750.0 700.0 650.0 Naphtha 150 200.0 230.0 350.0 400.0 Example 1 Prepare the main agent and hardener according to the following formula, mix well, and use three rollers respectively

Page 16 C: \ Program Files \ Patent \ li. Ptd 475097 5. Description of the invention (M) Grinding and dispersing by the grinder.

Main agent (g) Resin solution binding agent (I) 153.0 2 -fluorenyl- l- [4- (fluorenyl-thio) benzyl] -2- (1,4- -oxyl mouse terpine) -Propanol- 1-ο η 6.0 2,2-Dimethoxy-2-diphenylethylenedione 2.0 Benzoic acid-2-Dimethylamine ethyl ester 1.5 Diisopentyl hexaacrylate 15.0 Barium sulfate 50.0 Silicon dioxide 20.0 Aeros i1 -200 2.0 Modaflow 2100 1.0 Dcfoamer DC- 1000 (Deuchem Trading Co.) 1.5 Cyan vein 2.0 Pigment green-36 1.2 Pigment green-7 1.0 Para-phthalic acid 0.2 Acetic acid monoethyl ether glycol 10.0 Hardened Agent (g) YDCN-704 (South Asia) 5.0 PT-810 (Ciba-Geigy Co.) 15.0 Brominated bisphenol epoxy resin 5.0 Page 17 C: \ Program Fi1es \ Patent \ 1i. Ptd 475097 V. Invention Instructions (15) Diisopentyl hexaacrylate 5.0 Ac ros i1-200 1.0 Barium sulfate 10.0 Acetic acid monoethyl ether glycol 10.0 Napha-150 (China National Petroleum Corporation) 5.0 Mix and stir the main agent and hardener uniformly, screen print Method is to print the photosensitive coating on a printed circuit board with copper conductors, put it in an oven, and dry it at 80 ° C for 20 minutes. Then, cover the negative and expose it with an ultraviolet exposure machine with an exposure energy of 500 mJ / cm2, and then develop it with a 1.0% sodium carbonate solution to expose the conductor portion to be coated with solder, and then place the substrate in 15 In an oven at 0 ° C, the hardening time is 40 minutes, so the production of the solder resist is completed. The hardened solder resist was subjected to chemical resistance tests such as dichloromethane firing, 10% sodium hydroxide solution, and 10% hydrochloric acid solution, and then tested for hardness and adhesion. The results are listed in Tab 1 e 1. Example 2 A main agent and a hardening agent were prepared according to the following formula, and they were mixed uniformly, and were dispersed by a three-roller mill. Base agent (g) Resin solution binder (I) 153.0 2 -fluorenyl-1- [4- (fluorenyl-thio) benzene] -2- (1,4-oxazepine) -propane- 1-〇11 5.0

C: \ Program Files \ Patent \ li. Ptd Page 18 475097 V. Description of the invention (16) Benzoic acid-2-diamidine ethyl ester 1.5 Diisopentyl hexaacrylate 25.0 Barium sulfate 25.0 Talc 10.0 Ac ros i 1 R-972 1.5 Modaflow 2100 1.0 Defoamer DC- 1000 (Deuchem Trading Co.) 1.0 Rat vein 1.0 2 -Phenyl-4,5-dihydroxy-fluorenimidazole [2-Phenyl-4,5- di hydroxy-methyl imidazole (2PHZ)] 1.3 Pigment green-36 1.2 Pigment green-7 1.0 Hydroquinone 0.2 Acetic acid monoethyl ether glycol 5.0 Hardener (g) EPON 1001 (Shell Co.) 10.0 YX-4000 ( Shell Co.) 20.0 Brominated bisphenol epoxy resin 5.0 Hydroxy diisopentyl pentaacrylate 5.0 Aeros i1-200 1.0 Barium sulfate 20.0 Monoethyl ether acetate 10.0 Page 19 C: \ Program F i1es \ Patent \ 1i.ptd 475097 V. Description of the invention (17)

Napha-150 (China National Petroleum Corporation) 5.0 Mix and stir the main agent and hardener, and print the photosensitive coating on the printed circuit board with copper wires by the screen method, and put it in an oven at 80 ° Dry at C for 20 minutes. After the plate is cooled, cover the negative and expose with an ultraviolet exposure machine with an exposure energy of 500 mj / cm2, and then develop with 1.0% ^ (sodium solution to expose the intended coating. Place the conductor part of the solder, then put the substrate in an oven at 150 ° C, and the hardening time is 40 minutes. This completes the production of the solder resist. The hardened solder is subjected to dichloromethane, 10% hydroxide The chemical resistance test of sodium solution and 10% hydrochloric acid solution, and then the hardness and adhesion test, the results are listed in Tab 丨 e 1. Example 3 The main agent and hardener are prepared according to the following formula, mixed together, each three times Grinding and dispersing by roller grinder. Main agent (g) Resin solution binder (I) 153.0 2-fluorenyl-1- [4- (fluorenyl-thio) benzene] -2- (1,4-oxazepine ) _Propane_ 1-〇11 6.0 Phenylacetate-2-diamidine ethyl ester 1.0 Hydroxy diisopentyl pentaacrylate 20 .0 Barium sulfate 30.0 Silicon dioxide 5.0 Ae ros i1-200 3.0

C: \ Program Files \ Patent \ li. Ptd page 20 475097 V. Description of the invention (18)

Modaflow 2100 1.0 Defoamer DC-100 ◦ (Deuchem Trading Co.) 1.0 Cyanide 0.5 2-phenyl-4,5-dihydroxy · 曱 imidazole 2.0 Pigment green-36 0.1 Pigment yc11ow-139 0.6 Hydroquinone 0.2 Ethylene glycol monobutyl ether 10.0 Hardener (g) YDCN-704 (South Asia) EPON lOOKShell C〇 Bromine-containing bisphenol type ring seal ^ Resin triacrylic acid hydroxyisoprene-S purpose 5.0 10.0 5.0 5.0

Aeros i1-200 0.5 barium sulfate 10.0 ethylene glycol monobutyl _ 10.0

Napha-150 (China National Petroleum Corporation 10.0 Mix and mix the main agent and hardener, and print the photosensitive coating on the printed circuit board with copper wires by screen printing, and put it in an oven at 80 ° C Dry for 20 minutes. After the plate is cooled, cover the negative and expose with a UV exposure machine with an exposure energy of 55. Then develop with a 1.0% sodium carbonate solution to expose the conductor to be coated with solder.

Page 21 C: \ Program F i1es \ Patent \ 1i.ptd 475097

V. Description of the invention (19) points' Put the substrate into an oven at 150 ° C, and the hardening time is 40 minutes, and the production of the solder resist is completed. The hardened solder paste was subjected to chemical resistance tests such as two-gas sintering, 10% sodium hydroxide solution, and 1 Q% hydrochloric acid solution, and then subjected to hardness and adhesion tests. The results are listed in Tab 丨 e 1. Example 4 A main agent and a hardening agent were prepared according to the following formula, and they were mixed uniformly, and were dispersed by a three-roller mill. Base (g) Resin Solution Binding Agent (II) 153.0 2 -fluorenyl-1- [4- (fluorenyl-thio) benzene] -2- (1,4-oxazepine) -propane-1 -〇n 10.0 Phenylacetic acid-2-Diamidine ethyl ester 2.0 Hydroxy diisopentyl triacrylate · 10.0 Diisopentyl hexaacrylate 10.0 Barium sulfate 40.0-Talc 5.0 Aeros i1 -200 3.0 _Ξ_ ^^ ^ | Lu 2.0 Modaflow 2100 1.0 Defoamer DC- 1000 (Deuchem Trading Co ·) 1.0 Cyan pulse 2.0 Pigment green-7 1.0 Hydroquinone 0.2 Acetic acid monoethyl ether glycol 10.〇Page 22C : \ Program Files \ Patent \ li. Ptd 475097 V. Description of the invention (20) Hardener (g) EPON 1001 (Shell Co.) 10.0 EPON 1031 (Shell Co.) 5.0 PT-810 (Ciba-Geigy Co.) 15.0 Diisopentyl hexaacrylate 5.0 Aeros i 1 -200 1.0 Barium sulfate 10.0 Ethylene glycol monobutyl ether 10.0 N apha -15 0 (China National Petroleum Corporation) 5.0 Mix and mix the main agent and hardener evenly. The photosensitive coating is printed on a printed circuit board with copper conductors, and placed in an oven, and dried at 80 ° C for 2 0 After the plate has cooled, cover the negative and expose it with an ultraviolet exposure machine with an exposure energy of 600 mJ / cm2, and then develop it with a 1.0% sodium carbonate solution to expose the conductor part to be coated with solder, and then place the substrate Put it into an oven at 150 ° C, and the hardening time is 40 minutes, so the production of solder resist is completed. The hardened solder paste was tested for chemical resistance such as dichloromethane, 10% sodium hydroxide solution, and 10% hydrochloric acid solution, and then tested for hardness and adhesion. The results are listed in Tab 1 e 1. Example 5. A main agent and a hardener were prepared according to the following formula, mixed uniformly, and then dispersed by a three-roller mill.

C: \ Program F i1es \ Patent \ 1i. Ptd Page 23 475097 V. Description of the invention (21) Main agent (g) Resin solution binding agent (11) 153.0 2 -methyl-1-[4-(fluorenyl- Thio) benzene] -2-(丨, 4-oxazepine) -Bingyuan-1-〇η 5.0 2,2-dimethoxy-2-diphenylethylenedione 2.0 phenylarsonic acid-2 -Diammonium ethyl ester 1.0 Hydroxy diisopentyl pentaacrylate 10.0 Barium sulfate. 45.0 Silicon dioxide 5.0 Aerosil R-972 1.5 Modaflow 2100 1.0 Dcfoamer DC- 1000 (Deuchem Trading Co.) 1.0 Cyanoguanidine 2.0 Pigment green-7 1.0 p-Benzene dihydrate 0.2 Acetic acid monoethyl ether glycol 10.0 Hardener (g) YDCN-704 (South Asia) 10.0 YX-4000 (Shel1 Co.) 20.0 Brominated bisphenol epoxy resin 5.0 Diisopentahexaacetate hexaacetate 10.0 Aerosil-200 1.0 Round ill C: \ ProgramFiles \ Patent \ li.ptd Page 24 475097 V. Description of the invention (22) Barium sulfate 15.0 Acetic acid monoethyl ether glycol 10.0 Napha- 150 (China National Petroleum Corporation) 5.0 Mix and stir the main agent and hardener, and print the photosensitive coating on the printed circuit board with copper wires by screen printing. Dry in an oven at 80 ° C for 20 minutes. After the plate is cooled, cover the negative and expose it with an ultraviolet exposure machine with an exposure energy of 550 mJ / cn ^, and then use a 1.0% sodium carbonate solution. Develop and expose the conductor part to be coated with solder. Then put the substrate into an oven at 150 ° C, and the hardening time is 40 minutes. This completes the production of solder resist. The hardened solder resist was subjected to chemical resistance tests such as methylene chloride, 10% sodium hydroxide solution, and 10% hydrochloric acid solution, and then subjected to hardness and adhesion tests. The results are listed in T a 1 e 1. Example 6 A main agent and a hardener were prepared according to the following formula, and they were mixed uniformly, and were dispersed by a three-roller mill. · Main agent (g) Resin solution binding agent (IV) 153.0 2 f-based 1 [4- (methyl · thio) benzyl 2- (1,4-oxazepine) · Protonine_ι_〇η 8.0 Benzoic acid-2-diammonium ethyl ester 2.0 Carboxyl bisisoamyl diacrylate 5.0 Hydroxy diisopentapenta pentaacrylate _ ——... —-------— _ 15.0

475097 V. Description of the invention (23) Barium sulfate 70.0 Ae ros i1 R-972 1.0 Aluminium trioxide 2.0 Mod a flow 2100% 1.0 Dcfoamcr DC-1000 (Deuchem Trading Co.) 1.5 Cyanoguanidine 1.0 2 -Phenyl-4,5-dihydroxy-fluorenimidazole 1.0 Pigment green-36 1.2 Pigment green-7 1.0 Hydroquinone 0.2 Acetic acid monoethyl ether glycol 15.0 Hardener (g) EPON lOOKShel 1 Co.) 5.0 EPON 1031 (She 11 Co.) 5.0 PT-810 (Ciba-Geigy Co.) 10.0 YX-4000 (Shell Co.) 10.0 Hydroxydiisopentapentapentaacrylate 5.0 Ae ros i 1 -200 1.0 Barium sulfate 15.0 Acetic acid mono Ethylene glycol 10.〇N apha -1 5 0 (China National Petroleum Corporation) 5.0 Yuan 11111 Page 26 C: \ Program Files \ Patent \ li.ptd 475097 V. Description of the invention (24) Mix the main agent and hardener Stir evenly, print the photosensitive coating on the printed circuit board with copper wires by screen printing, put it in an oven, and dry it at 80 ° C for 20 minutes. After the plate is cooled, cover the negative And exposed with an ultraviolet exposure machine, the exposure energy was 5 50 niJ / cm2, and then 1.0% sodium carbonate Was developed, the exposed conductor to be coated portion of the solder, and then placed in an oven substrate 1 5 0 ° C, the curing time of 40 minutes to complete the production namely as the solder resist. The hardened solder resist was tested for chemical resistance such as dichloromethane, -10% sodium hydroxide solution, and 10% hydrochloric acid solution, and then tested for hardness and adhesion. The results are listed in Tab 1 e 1. Example 7 A main agent and a hardening agent were prepared according to the following formula, and they were mixed uniformly, and were dispersed by a three-roller mill. Main agent (g) Resin solution binding agent (V) 153.0 2 -Methyl-1-[4-(fluorenyl-thio) benzene j-2- (1,4-oxazepine land) -propane-1- on 8.0 Phenylacetate-2-diammonium ethyl ester 2.0 Hydroxydiisopentapentapentaacrylate 15.0 Epoxy acrylate (synthesized by reaction of DEN-438 (Shell Co.) and acrylic acid) 20.0 sulfuric acid Barium 30.0 Silicon dioxide 15.0 Aerosil R-972 2.0 Modaflow 2100 1.0

C: \ Program Files \ Patent \ li. Ptd Page 27

475097 I V. Description of the invention (25) Defoamer DC-iOOO (Deuchem Trading Co.) 1.0 Cyanoguanidine 2.0 Pigment green-36 1.2 Pigment green-7 1.0 Hydroquinone 0.2 Acetic acid monoethyl ether glycol 10.0 Hardener (g) EPON 1001 (Shell Co.). 10.0 PT-810 (Ciba-Geigy Co.) 10.0 Brominated bisphenol epoxy resin 15.0 Ae ros i 1 -200 1.5 Barium sulfate 10.0 Ethylene glycol mono Butyl ether 10.0 Napha-150 (China National Petroleum Corporation) 5.0 Mix and stir the main agent and hardener, and print the photosensitive coating on the printed circuit board with copper wires by screen printing method, and put it in the oven. Dry olefin 'was performed at 0 C for 20 minutes. After the plate was cooled, the negative was covered and exposed with an ultraviolet exposure machine with an exposure energy of 450 mJ / cm2, and then developed with a 1.0% sodium carbonate solution to expose the desired After coating the conductors of the solder, the substrate is placed in an oven at 150 ° C, and the hardening time is 40 minutes. If this is the case, the production of the solder resist is completed. The hardened solder resist is tested for chemical resistance such as dioxane, 10% sodium hydroxide solution and 10% hydrochloric acid solution.

475097 V. Description of the invention (26) The results are listed in the Table test, and then tested for hardness and adhesion. Example 8 The following formulations were mixed uniformly, and then dispersed with a three-roller mill (triple-rm 1 1). Composition of photoresist (g) Resin solution binder (III) 167.0 2-methyl-bu [4-(fluorenyl-thio) benzene] _2- (1,4-oxazepine) -propane- 1-on 3.0 2,2 -dimethoxy-2-diphenylethylene di. 1.0 benzoic acid 2-diamidine ethyl ester 0.5 triacryl triisopropylammonium triethyl ether 60.0 Pentapentaester 15.0 Talc 20 Aeros ί 1 -200 0.5 Defoamer DC-1000 (Deuchem Trading Co.) 0.5 Leuco crystal violet 1.3 Hydroquinone 0.2 Acetic acid monomethyl ether propylene glycol 40.0 The photosensitive coating is printed on a copper foil substrate and placed in an oven, and dried at 80 ° C for 10 minutes. After the plate is cooled, the negative is covered and exposed with an ultraviolet exposure machine. The exposure energy is 丨 〇〇 in j / cm2, the photosensitive layer is developed with a 1.0% sodium carbonate solution, and then the exposed steel conductor is engraved with a cuprous chloride solution, and finally, 3% hydrogen and oxygen at 50 t

Page M: C: \ Program Files \ Patent \ li.ptd 475097 V. Description of the invention (27) The sodium chloride solution is peeled off to complete the production of the printed circuit board wires. The results of the resolution tests are listed in Table 1.

Tab 1 e 1 Performance of liquid solder resist Example 1 2 3 4 5 6 7 8 Resolution (#m) 50 μm 50 // m 50 // m 50 μm 50 // m 50 // m 50 25 ym Property of solution (CH2CI2) ^ 20min ^ 20min ^ 20min ^ 20min ^ lOmin ^ 20min ^ 20min-and chemical properties (10%, sodium hydroxide) ^ lOmin ^ lOmin ^ lOmin ^ 10min ^ 5nnn ^ 10min ^ lOmin-Chemical resistance (10%, hydrochloric acid) ^ lOmin ^ lOmin ^ 10min ^ 5min ^ 10min ^ lOmin ^ lOmin-Hardness 6H 6H 6H 5H 6H · 6H 6H • Adhesion (after 260 ° C, hot ai r leveling) 100% 100% 100 % 100% 100% 100% L " ^ ~ ——--- 100% -------Based on the results of the above comparisons, we can know that the foregoing and other objects and features of the present invention are better implemented through the above. The description of the examples will be more obvious. This description is only for the purpose of illustrating the invention in a better condition, rather than trying to limit the scope of the invention, and other modifications made in the spirit of the right ... And changes belong to the guarantee of the present invention ~ Ⅹ

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Claims (1)

475097 (a) — film-forming polymer, which is prepared by reacting the following reactants: (1) a styrene-marine anhydride resin, which is composed of styrene and mapin anhydride in a ratio of 3.1 to 1. _ 3 is formed by ♦ proportion polymerization, and its molecular weight is between 8 0 and 1 0 0 0 0 0; (ii) An unsaturated compound that contains at least one meridian group and three acrylic functional groups, and has an acid anhydride group equivalent ratio to the above phenothyl moth-malein anhydride resin ranging from 1: 0.2 to 1 · · 〇 Between 7; (iii) saturated alcohols having an anhydride group equivalent ratio to the above acetophen-malein anhydride resin of between 1: 1 and 1 to 1:10; (b) photoinitiator ; And 2. 3. 4. (c) unsaturated photocrosslinking monomer. For example, the photosensitive composition of claim 1 wherein the 'unsaturated compound contains a hydroxyl group and an acrylic functional group. For example, the photosensitive composition according to item 1 of the patent application range, wherein the 'unsaturated compound is a triacrylate iso / triester. For example, the photosensitive composition of the first patent application range, wherein the 'unsaturated compound contains a hydroxyl group and five acrylic-guan' energy groups. As in the photosensitive composition in the scope of patent application item 1, wherein the 'unsaturated' The compound is pentaacrylate-based diisopentapentyl ester. For example, the photosensitive composition in the first patent application range is an alkyl alcohol. & Photosensitive composition in the scope of patent claim 1, wherein saturated alcohol Containing ether groups—Case No. 87116320 Shen Qing Patent Scope Female Shen Qing Patent Scope The first category is ethyl alcohol, which is a photosensitive composition of '纟 中' saturated alcohol, butanol, and butyl alcohol. N-propanol, iso-propanol, n-hexanol, n-heptanol, 1-pentanol, fluorenyl alcohol, iso-heptanol, n-butyl alcohol and cyclohexanol. Types are ether alcohols, which are the photosensitive compositions of the author. Among them, saturated alcohols, e, self-alcohols such as ethoxyethanol, ethoxyethylpropane-coated ethanol, diethylene glycol ether , Methoxypropanol, and diglycerol ether. … · 10. For example, the second component of the photosensitive composition of the patent application No. 1 is the ethane resin per tick. The secondary components of the photosensitive composition of item k of the patent are% oxyethane resin and hardener. • For example, I, the photosensitive composition according to item 16 of the patent, wherein the hardened 13 shell is a cyanoguanidine or an imid compound. ··· The photosensitive composition according to item 16 of the patent application range, wherein the hardening agent 14 is a cyanoguanidine or an imid compound. • t, the secondary component of the photosensitive composition in item 1 of the patent is cyclocyanoacrylate. 15. If the photosensitivity product of item J8 of the patent scope is requested, the epoxy · acrylic acid ester is the reaction product of phenol ~ aldehyde resin type epoxy resin and acrylic acid. Amendment_ The scope of patents for the six or ten mouths is the first. The all-resin type epoxy resin is the first. Page 33 2001.06.27. 033