TW494276B - Solder resist ink composition - Google Patents

Abstract

A solder resist ink composition for printed circuit boards which is suitable for forming, with satisfactory adhesion, a primer deposit layer, e.g., an Ni-Au deposit layer, having satisfactory wettability by a solder. The composition comprises (A) a photosensitive prepolymer having a carboxyl group and at least two ethylenically unsaturated bonds per molecule and having an acid value of 50 to 150 mg-KOH/g on a solid basis, (B) a photopolymerization initiator having a melting point of 100 DEG C or higher, (C) a diluent, and (D) a thermosetting ingredient comprising as the main component an epoxy compound having two or more epoxy groups per molecule.

Description

494276 A7 __ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1) The technical field to which the invention belongs The invention relates to a solder resist ink composition, and more specifically, it can satisfy the solder heat resistance It is suitable for printed circuit boards that have the characteristics required for soldering materials such as the adhesion of circuit boards, and is suitable for stable supply and the formation of a good pad with good wettability. Composition of solder-resistant ink. Prior art Recently, with the rapid advancement of semiconductor parts, there is a tendency to make electronic devices compact, lightweight, high-performance, and multifunctional. Along with this trend, printed circuit boards have also become increasingly dense and surface-mounted. In the manufacture of high-density printed circuit boards, optical solder resists are generally used, and dry film-type optical solder resists and liquid optical solder resists have been developed. For example, Japanese Unexamined Patent Publication No. 5 7-5 5 9 1 4 of a dry film-type optical solder resist discloses a linear polymer containing a urethane di (meth) acrylate and a specific glass transition temperature. A photosensitive resin composition for a dry film composed of a compound and a photosensitizer. However, such dry film-type solder-resistant materials lack reliability due to insufficient solder heat resistance and insufficient adhesion to circuit boards, and therefore they are practically unused. On the other hand, the liquid optical solder resist is disclosed in JP 6 1-2 4 3 8 6 9 and it is disclosed that the reaction product of a phenol lacquer type epoxy compound and an unsaturated monocarboxylic acid is saturated or not. Saturated polybasic acid anhydride-reactive active energy ray-curable resin, photopolymerization initiator, diluent, and epoxy compound consisting of light-curing and thermosetting liquid (please read the precautions on the back before I · I. ΐΛ ^ Pages:.-Line · This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -4- 7 (42 49 A7 _____B7___ V. Description of the invention (2) Photoresist ink composition This composition satisfies the above-mentioned characteristics required for being solder-resistant, that is, it can satisfy the solder heat resistance and adhesion to circuit boards, etc. However, a solder-resistant material using such a composition is useful for forming this resistance. When the conductor pad (soldering pad) of the solder is subjected to the collision of the solder and the solder is supplied, the adhesion of the conductor to the solder is poor, and it is expected to improve it. In particular, in order to improve the bonding of the solder body to the conductor pad, After the formation of solder resistance (or solder resistance Front), in the case of electroless plating (head plating) on the surface of the conductor pad, poor adhesion between the conductor pad and the electroless plating and / or between the electroless plating and the flux body, especially the conductor The tendency of poor adhesion between the pad and the electroless plating is remarkable. The problem to be solved by the invention is, therefore, the purpose of the invention is to provide a solder resistant material which can satisfy the solder heat resistance and the adhesion to the circuit board. Requires characteristics and is suitable for conductor pads with good wettability of the solder body, that is, printed circuit boards with good adhesion to the first-layer plating such as the Ni-Au layer with good wettability of the solder body. In order to achieve the foregoing object, according to the present invention, a solder resist composition is provided for forming a solder resist on a printed circuit board formed with a lead plating layer formed on a surface of a conductor pad. (1) A photosensitive prepolymer having a carboxyl group and at least two ethylenically unsaturated bonds in one molecule, and a solid component having an acid value of 40 to 150 mg KOH / g, (B) Melting point is more than 100t Zhang scale is applicable to China National Standard (CNS) A4 (210 χ 297 mm) (Please read the precautions on the back before ϋ 1 1 ϋ mmmt ϋ One (WJ · n · ϋ ϋ n ϋ 1 ϋ I ϋ 9 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives -5- 27 94 4 A7 ___B7 ___ V. Description of the Invention (3) Photopolymerization initiator, (C) Diluent, and (D) Two or more epoxy resins in one molecule Based on the thermosetting component of the main epoxy compound as the main component, a solder resist ink composition is featured. In a preferred embodiment, the aforementioned photopolymerization initiator (B) uses 2-benzyl-1, 2-dimethyl Amine mono (4-morpholino benzyl) -1 monobutane-1-one and / or bis (; y5-.2,4 monocyclopentadiene-1 1-yl) bis (2,6-difluoro-1 3- (1H-pyrrole-1-yl) phenyl) titanium 0 In a more specific aspect, the diluent (C) may use a photopolymerizable vinyl-based monomer and / or an organic solvent, and the heat The curable component (D) preferably further contains an epoxy curing accelerator. Embodiments of the invention The present inventors have found that the poor bonding of the solder body to the conductive pad is caused by the fumes generated when the solder-resistant material is dried or post-ageed, or during the baking process after the head layer is plated. The generated smoke is attached to the substrate, especially to the conductor pad. Further, it was found that the smog adhered to the conductor pad of the substrate was caused by the evaporation of the photopolymerization initiator caused by the heating. Based on such findings, the present inventors have repeatedly worked hard to achieve the aforementioned object, and found that if a photopolymerization initiator (B) having a melting point of 100 ° C or higher is used, the solder resist is prevented from drying or post-aging. , Or the smoke generated during the baking process after the first pass plating can be on the conductor pad, so that the first pass plating such as the Ni-Au layer with good wettability of the solder body can form a good adhesion, Furthermore, the adhesion of the solder body to the conductor pad can be improved. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-6-494276 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs_B7___ V. Description of the Invention (4) That is, the photopolymerization initiator (B) used in the present invention It has a high melting point ', so it will not evaporate at the temperature (approximately 60 ~ 100 ° C) when the coating film of the aforementioned composition is dried, and the temperature (approximately 1 40) ~ 150 ° C) will not evaporate, so the amount of smoke generated is very small. Therefore, if the composition of the present invention is used, a photoresist film is formed without contamination of the substrate due to smog, and a lead plating layer such as a Ni-Au layer can be formed on the surface of the conductor pad with good adhesion. In addition, the hardened coating film of the aforementioned composition does not evaporate even during the baking treatment after the head pass plating, so the wettability of the head pass plating layer and the solder body is good. Furthermore, even when exposure is performed in a contact manner (when a patterned photomask is formed and active light is selectively irradiated), the coating film of the photoresist composition does not adhere to the photomask. As a result, it has (i) improved workability, (i) no contamination of the mask caused by volatile fumes, (iii) can suppress the use of expensive photopolymerization initiators, and can add more photopolymerizable monomers, Therefore, the effects such as light curing characteristics can be greatly improved. The photopolymerization initiator (B) having a melting point of 100 ° C or more may be used alone or in combination of two or more known and commonly used photopolymerization initiators, and preferably 2-benzyl-2-dimethylamino-1_ ( 4 monomorpholine benzyl) -butane-one-one and / or bis (7-5-2,4-cyclopentadiene-1 1-yl) bis (2,6 -difluoro-2-(1H- Pyrrole-1-yl) phenyl) titanium. The photopolymerization initiator (B) is N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl Tertiary amines such as 4-A-dimethylaminobenzoate, triethylamine, triethanolamine, etc. are well known. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (please read the back first) (Note 5 and 5 more pages)

II ϋ ϋ ϋ ϋ I ^ 1 ^ eJ H 1 n II ϋ II ϋ H > 1 ϋ ϋ ϋ ^ 1 ϋ I ^ 1 II n I ϋ ϋ ϋ ϋ ϋ I ϋ · 9 494276 A7 B7 V. Description of the invention ( 5) It is customary to use one or a combination of two or more types of light sensitizers. These light-sensitized consumer cooperatives printed by the Intellectual Property Bureau of the Ministry of Economic Affairs preferably have a melting point of 100 t or more. That is, the above-mentioned photopolymerization initiator (B) is formulated in a proportion of 1,000 parts by weight of the photosensitive prepolymer (A), and preferably 5 to 25 parts by weight. When the amount of the hair conditioner (B) is less than the above range, the properties are deteriorated, and when the amount is too large, it is not good as a solder resist. According to the process of containing the composition of the present invention having a melting point of 100 ° C and (B) according to the above, it can be shown that, as in the previous aspect, the photocuring coating film of the composition of the present invention is cured. The heating temperature is heated, and then the aforementioned thermosetting component (and reacts with the aforementioned photosensitive prepolymer having a carboxyl group to obtain a solder-resistant film having excellent properties as described above. The solder-resistant component of the present invention will be described in detail below. The aforementioned photosensitive prepolymer (A) can be used for a carboxyl group and at least two ethylenically unsaturated bonds, and has a well-known and commonly used susceptor or polymer of ~ 150 mg · KOH / g). For example, (1) Make two or more cyclic compounds (hereinafter referred to as epoxy resin (a) and) in one molecule to perform an esterification reaction (full or partial esterification, in a proportion relative to the first 1 to 30 weight) The reason is that the photo-hardening of the composition causes the photo-hardening of the composition to decrease as described above. The effect of the photo-polymerization initiator described above, and the heat-curing (post-component (D) melting point D) is softened and melted. A) the components that cause cross-linking of the ink composition In one molecule, the type has both an acid value of 40 and a light prepolymer (a polyfunctional epoxy-unsaturated monocarboxylic acid of oligomeric oxy group (b is preferably fully esterified). Please read the back first. · Attention

Item I to I m Page I The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8-42 49 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __ V. Description of the invention (6 ) And make the hydroxyl group of the esterified product react with a saturated or unsaturated polybasic anhydride (c) with a solid component acid value of 50 to 150 mg K 0 H / g, and (2) make ( Copolymer of (meth) acrylic acid and other copolymerizable monomers (d) having ethylenically unsaturated bonds. The solid component has an acid value of 50 to 150 mgKOH / g, and partly is (meth) acrylic acid. The glycidyl ester reaction is preferably a resin having a weight average molecular weight in the range of 5,000 to 20,000. (3) Let glycidyl (meth) acrylate and other copolymerizable monomers having an ethylenically unsaturated bond. (D) copolymer, the unsaturated monocarboxylic acid (b) is reacted, and the hydroxyl group of the obtained reaction product is saturated or unsaturated with a solid component acid value of 50 to 150 mgKOH / g The polybasic acid anhydride (c) is preferably obtained from the anti-acne tree having a weight average molecular weight in the range of 5,000 to 20,000. (4) Make the polyfunctional epoxy resin (a), and unsaturated monocarboxylic acid (b), and have at least two hydroxyl groups in one molecule, and one other than the hydroxyl group that reacts with epoxy groups The reaction product (I) of the base compound (e) is a resin obtained by reacting with a saturated or unsaturated polybasic anhydride (c), (5) an unsaturated polybasic anhydride such as styrene and the like having a vinyl group such as styrene Copolymers of aromatic hydrocarbons, unsaturated polycarboxylic acid resins such as resins obtained by reaction with hydroxyalkyl (meth) acrylate, and (6) the above reaction product (I) and saturated or unsaturated Polybasic acid I ϋ ϋ ϋ 1 —ϋ ϋ ϋ 1: 0, I — n ϋ (Please read the precautions on the back before JR page) I. · Line _ 瓤 ----------- ------------ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -9-494276 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (7) The unsaturated polycarboxylic acid urethane resin etc. which are reaction products, such as an anhydride (C) and an unsaturated monoisocyanate (f), can be used suitably. However, the photosensitive prepolymer is not limited to the foregoing, and if it has both a carboxyl group and at least two vinyl unsaturated bonds in one molecule, and the solid component has an acid value of 40 to 150 mg of KOH / g of photosensitive prepolymer can be used in the present invention. Alas, in this specification, the term "(meth) acrylic acid" is used for the general term acrylic acid, methacrylic acid, and mixtures thereof. The same applies to other similar expressions. As described above, the photosensitive prepolymer (A) imparts a lot of free carboxyl groups to the side chain of the main chain polymer. Therefore, the composition containing the photosensitive prepolymer can be developed through a dilute aqueous alkali solution, and simultaneously After exposure and development, the coating film is heated, and an additional reaction can be caused between the epoxy group of the epoxy compound as the thermosetting component (D) and the free carboxyl group of the chain to obtain heat resistance and resistance. Solvent resistance, acid resistance, adhesion, resistance to electroless gold plating, electrical properties, hardness and other excellent solder resistance films. The aforementioned epoxy resins (a) used in the resin synthesis of the aforementioned (1) and (4) may be used alone or suitable for two or more types of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol. Epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, biphenol epoxy resin Well-known and commonly used epoxy resins such as bixylenol type epoxy resin, trisphenol methane type epoxy resin, N-glycidyl type epoxy resin and the like. These epoxy resins are also phenolic lacquer type epoxy resins such as phenol novolac lacquer type, cresol novolac lacquer type, and bisphenol A phenolic lacquer type, because they are available (please read the precautions on the back before I ___ Page 1 ------ Order-! I--I · Line — The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -10-494276 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer cooperatives printed acid dimers, methacrylic acid, crotonic acid, and / or reactants of unsaturated dibasic acid anhydrides and acrylates, glycidyl compounds white inverse acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride , Methyl tetrahydrophthalic anhydride, anhydride or other saturated or unsaturated di, hydroxypropyl methyl (meth) acrylate) polyethylene glycol methacrylate trimethylol acrylate, penta (meth) propylene, etc. (Meth) acrylic acid esters, such as iso- and unsaturated dibasic acids (such as acid, tetrahydrophthalic acid, itaconic acid-based compounds, etc.) can be used alone or in combination. From the viewpoint of photohardenability, the aforementioned (1), (3 Or unsaturated poly A7 —- _ B7__ 5. Description of the invention (8) The solder-resistant film with excellent heat resistance and chemical resistance, etc., is particularly good. Secondly, the aforementioned (1), (3) and (4) ) Specific examples of the unsaturated monocarboxylic acid (b) used in resin synthesis include, for example, acrylic acid, acrylic acid, Θ-styryl acrylic acid, Θ-fur alpha-cyanocinnamic acid, cinnamic acid, etc. (Methyl) or saturated or unsaturated dibasic acids and unsaturated monobasic product half esters having one hydroxyl group, such as succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid, itaconic anhydride, Methylmethylenetetrahydrophthalic acid anhydride, and hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, mono (ester, glyceryl di (meth) acrylate, (propane ester, Tri (meth) acrylic acid pentaerythritol dipentaerythritol ester, phenyl glycidyl ether and the like having one hydroxyl group (half ester obtained by reacting methyl ester ratio), or, saturated, succinic acid, malay Acid, adipic acid, phthalic acid, fumaric acid, etc.) and unsaturated monoglycidyl Semi-esters, etc. These unsaturated monocarboxylic acids are more than two kinds. Among these unsaturated monocarboxylic acids, acrylic acid or methacrylic acid is also preferred.), (4) and (6) in the resin synthesis of alkaline anhydride (c The representative of) can be listed as the standard of Chinese paper (CNS) A4 (210 X 297 mm).

Order-11-494276 Α7 B7 V. Description of the invention (9) Acid anhydride, acetic anhydride, itaconic anhydride, acetic anhydride, tetrahydrofluoric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylenetetrahydro Dibasic acid anhydrides such as phthalic anhydride, methylmethylenetetrahydrophthalic anhydride, chlorobutanol anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, etc. Aromatic polyvalent carboxylic anhydride; others are attached, for example, 5-(2,5 -dioxytetrahydrofuran)-3 -methyl-3 -cyclohexylene-1, 2-dicarboxylic anhydride. Valent carboxylic anhydride derivatives and the like. These saturated or unsaturated polybasic acid anhydrides (c) may be used singly or in combination of two or more kinds. Among these polybasic acid anhydrides, tetrahydrophthalic acid, hexahydrophthalic acid, and succinic anhydride are particularly preferable from the viewpoint of the characteristics of the hardened coating film. The use ratio of these polybasic acid anhydrides (c) is preferably such that the solid component acid value of the reaction product is in the range of 40 to 150 mgKOH / g. When the acid value of the produced photosensitive prepolymer is less than 40 mg KOH / g, the alkali solubility is deteriorated, and it is difficult to develop a coating film of the resulting composition with a dilute alkaline aqueous solution described later. 'Another * In terms of the right side, if it exceeds 15 OmgKOH / g, the photo-hardening film's development resistance, alkali resistance, and electrical properties will be reduced as photoresistors, and it may not be used as solder resistance, so they are not good. Representative examples of other copolymerizable monomers (d) having ethylenically unsaturated bonds used in the resin synthesis of the above (2) and (3) include styrene, chlorostyrene, and α-methylstyrene; Substituents are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, third butyl, pentyl, 2-ethylhexyl, octyl, decyl, nonyl, dodecane Hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl The paper size of this paper is based on China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first, and then the page) Order --------- line 丨 鬌 The intellectual property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives-12- 494276 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (10) Substituted acrylate or methacrylate; Polyethylene glycol monoacrylate or mono Monoacrylate or monomethacrylate of methacrylate, or polypropylene glycol; vinyl acetate, vinyl butyrate, or benzyl Vinyl esters; acrylamide, methacrylamide, N-methylolpropanamide, N-methylolmethacrylamide, N-methoxymethacrylamide, N-ethoxymethylpropene Ammonium amine, N-butoxymethacrylamide; acrylonitrile or maleic anhydride. These copolymerizable monomers (d) can be used alone or in combination of two or more kinds. Among these copolymerizable monomers, in terms of the glass transition temperature T g and cost of the obtained copolymer resin, styrene and (meth) propylene 2-hydroxyethyl ester and (meth) acrylate are used as good. In terms of light transmittance in the coating film, it is more preferable to use methyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate which do not contain a benzene ring. The weight average molecular weight of the resins (2) and (3) is preferably in a range of 5,000 to 20,000. When the weight average molecular weight is less than 5,000, it is difficult to obtain hardened coating film characteristics such as heat resistance of the solder. On the other hand, when the weight average molecular weight exceeds 20,000, it is difficult to display the diluted alkaline aqueous solution. For example, I am afraid that it cannot be used as a solder resist. The synthetic reaction of the resin of (4) is to make the polyfunctional epoxy resin (a) react with unsaturated monocarboxylic acid (b) (or compound (e)), and then use compound (e) (or unsaturated monocarboxylic acid) The first method of the acid (b)) reaction and the second method of simultaneously reacting the polyfunctional epoxy resin (a) and the unsaturated monocarboxylic acid (b) with the compound (e). Although either method is acceptable, the second method is preferred. The above reaction is for epoxy group 1 of polyfunctional epoxy resin (a) (please read the precautions on the back first and then page II) --------- line — 9 -ϋ n ϋ ϋ ϋ n- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -13- 494276 A7 B7 V. Description of the invention (11) Equivalent, the total of unsaturated monocarboxylic acid (b) and compound (e) The amount is about 0.8 ~ 1.3 mole ratio reaction is preferred, and particularly preferred is the reaction is about 0.9 ~ 1.3 mole ratio. Unsaturated monocarboxylic acid (b). Compound (e) The use ratio is 1 mol relative to the total amount of the unsaturated monocarboxylic acid (b) and the compound (e), and the use amount of the compound (e) is preferably from 0.05 to 0.5 mol, and particularly preferably Mol is from 0.1 to 0.3. Second, the reaction between the reaction product (I) and the polybasic acid anhydride (c) is based on the hydroxyl group in the reaction product (I). A polybasic anhydride (C) reaction of ~ 0 · 9 equivalents is preferred. On the other hand, the synthesis reaction of the polycarboxylic acid urethane resin containing an unsaturated group in the aforementioned (6) is to make the aforementioned reaction yield (1) Reaction with polybasic acid anhydride (c), and secondly, the unsaturated isocyanate (f) containing polyunsaturated polycarboxylates containing the unsaturated product relative to the reaction product (I) and polybasic anhydride (c) The hydroxyl group in the acid resin is preferably reacted with an unsaturated monoisocyanate (f) containing an unsaturated group in an amount of 0.05 to 0.5 equivalents per 1 mole of the hydroxyl resin. The resin synthesis of the aforementioned (4) and (6) Specific examples of the compound (e) having at least two hydroxyl groups in one molecule and one reactive group (for example, a 'carboxyl group, a secondary amine group, etc.) other than the warp group which reacts with an epoxy group may be used. Examples of polycarboxylic acid-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylhexanoic acid; diethanolamine, Isopropanolamines and other second-ment alcohol amines, etc. These compounds (e) can be used alone or in combination of one or more. The best is (Please read the precautions on the back before ordering --------- line -9 The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 210 X 297 mm) -14 · 494276 A7 ___ B7 V. Description of the invention (12) Dimethylolpropionic acid, etc. (Please read the precautions on the back first, and then, the specific examples of the aforementioned unsaturated monoisocyanate (f) Examples thereof include methacrylic acid isocyanate, methacrylic acid isocyanate, and organic diisocyanates (for example, cresyl diisocyanate, ditolyl diisocyanate, and diisocyanate). Isophorone ester, adiisocyanate diisocyanate, and the like) and (meth) acrylic acid esters having one hydroxyl group in the aforementioned molecule, and reactants obtained by reacting at about the same molar ratio. These unsaturated monoisocyanates (f) can be used alone or in combination of two or more. Next, as the diluent (c), a photopolymerizable vinyl-based monomer and / or an organic solvent can be used. --Line- Representative materials of photopolymerizable vinyl monomers printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economics include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; B Mono- or diacrylates of glycols such as diols, methoxyglycol, polyethylene glycol, propylene glycol, etc., N, N-dimethylacrylamide, N-hydroxymethacrylamine, N , Acrylamides such as N-dimethylaminopropylacrylamide, amine alkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; Polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and trihydroxyethyl isocyanate, or polyvalent acrylic esters thereof such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylic acid Esters, bisphenol A diacrylates, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane tri Acrylates of glycidyl ethers such as glycidyl ether, triglycidyl isocyanate, etc .; and C Melamine enoate, and / or each methacrylate corresponding to the aforementioned acrylate, and the like. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -15- 494276 A7 B7 V. Description of the invention (13) The organic solvents mentioned above can be ketones such as methyl ethyl ketone and cyclohexanone Aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl Glycol ethers such as ethers, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, and acetate esters of the above glycol ethers; ethanol , Alcohols such as propanol, diethanol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. It is preferred that the photosensitive prepolymer (A) has good compatibility and does not dissolve the thermosetting component (D). The diluent (C) as described above can be used alone or in a mixture of two or more types. The preferred range of the amount of the diluent used is' When using a photopolymerizable monomer, it is preferably 40 parts by weight or less based on 100 parts by weight of the photosensitive prepolymer (A), and when it is more than that, It is unfavorable because it deteriorates the touch dryness. On the other hand, the use amount of the organic solvent is not limited to a specific ratio, but it is appropriate for the photosensitive prepolymer (A 1 〇. 〇 by weight to be in a range of about 30 to 300 parts by weight). It is appropriately set according to the selected coating method. The purpose of using the diluent (C) is to dilute the photosensitive prepolymer in the case of a photopolymerizable vinyl monomer, and to make it easy to apply, and Enhance photopolymerization. On the other hand, in the case of an organic solvent, a photosensitive prepolymer is dissolved and diluted, and is applied in a liquid form, followed by drying and forming a film, so that exposure can be achieved. Therefore, according to The thinner used can be the contact method or non-contact method to make the photoresist tightly adhere to the film. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first) Page I Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ϋ n 1 1_1 a a ϋ 1 * II ϋ III ϋ · ϋ l_i 1. 1 1 n I · nn nn a__i I 1_1 ϋ n 16-494276 Ministry of Economic Affairs Intellectual Property Bureau Employee Consumption A7 B7 printed by Sakusha Co. 5. Any of the exposure methods of the invention description (14). Second, the thermosetting component (D) is an epoxy compound containing one or more epoxy groups in one molecule. Such epoxy compounds Examples of the bisphenol S type epoxy resin include EBPS-2000 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., and Epiclone EXA -1 5 1 4 manufactured by Dainippon Ink Chemical Industry Co., Ltd. ; Phthalic acid diglycidyl ester resins such as Blenmer-DGT manufactured by Japan Oil & Fat Co., Ltd .; heterocyclic epoxy resins such as TEPIC series manufactured by Nissan Chemical Industry Co., Ltd. and Araludite PT8 1 0 manufactured by Ciba Specialty Chemicals; YX-4 0 0 0 bis xylenol type epoxy resin made by Shell Epoxy Co., Ltd., and YL-6 0 5 6 bis phenol type epoxy resin made by Shell Epoxy Co., Ltd .; Toto Kasei Co., Ltd. ) Tetraglycidyl dimethyl ether resin made of ZX-1 0 6 3, etc., is equivalent to hardly soluble epoxy resin in diluent. Epicote made by Petrochemical Shell Epoxy Co., Ltd. 1 0 0 9, 1 0 3 1. Epiclone N -3050 manufactured by Dainippon Ink Chemical Industry Co., Ltd. N-7050, N-9050, AER-664, AER-667, AER-669, manufactured by Asahi Kasei Corporation, YD-012, YD-014, Todo Chemical Co., Ltd., YD-017, YD-〇2〇, YD-002, Ciba * Specialty Chemicals XAC — 5 0 5, GT — 7004, 6484 D, 6099, Dow Chemical Company DER — 642U, DER — 673MF, Solectron Industries (the paper size of the company applies Chinese national standards (CNS) A4 specification (210 X 297 public love) --1 · 1 1 ϋ ϋ 1 ^ OJ I .1 n ϋ I ϋ I ϋ j (Please read the precautions on the back before this page) 1 -17- 494276 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Inventory (15)) Double-type epoxy resins made of EP-5400, EP-5900, etc .; ST-2004, ST — 2 manufactured by Tohto Kasei Co., Ltd. 〇7 and other hydrogenated bisphenol A-type epoxy resin; Totsuka Kasei Co., Ltd., YDF — 2004, YDF — 2007 and other double 酣 F-type epoxy resin; Sakamoto Pharmaceutical Industry Co., Ltd. SR-BB s, SR _ TBA — 400, Asahi Chemical Industry Co., Ltd. 51? — 62, EP — 66, Asahi Chemical Industry Co., Ltd. AER-755, AER — 765 Brominated bisphenol A epoxy resins manufactured by Tohto Kasei Co., Ltd. YDB-600, YDB — 7 1 5; EPPN-201, E〇CN — 103, E〇CN — manufactured by Nippon Kayaku Co., Ltd. 1020, E〇CN— 1025, ECN-278, ECN-292, ECN-299, Ciba Specialrty Chemicals, ECN — 1 2 7 3. ECN — 1299, Todo Chemical Co., Ltd. YDCN — manufactured by Asahi Kasei Corporation — 220L, YDCN-220HH, YDCN-702, YDCN-704, YDPN—601, YDPN-602, Epiclone N—673, N-680, N-695, N-770, N-, manufactured by Dainippon Ink Chemical Industry Co., Ltd. 7 7 5 and other phenolic lacquer type epoxy resins; EPX-8001, EPX-8002 manufactured by Asahi Denka Kogyo Co., Ltd .; EPPX-8060, EPPX—8061, Epiclone N — 8 8 manufactured by Dainippon Ink Chemical Industry Co., Ltd. No. 0 bisphenol A phenolic lacquer-type epoxy resin; EPX-4 9-60, E PX-4 9-3 0, etc. manufactured by Asahi Denka Kogyo Co., Ltd .; Todo Chemical ( Strains (Please read the precautions on the back before page I

IIIIII ^^ · 1111111 ^^ I The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 494276 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Invention Description (16)) YDG — 4 1 4 and other glyoxal type epoxy resins; YH 1402, ST — 110 made by Toto Kasei Co., Ltd., YL 9 3 1 and YL 9 3 3 made of Petrochemical Shell Epoxy Co., Ltd. Epoxy resins containing amine groups; Epiclone TSR — 601 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPX — 84 — 2 manufactured by Asahi Denka Kagaku Kogyo Co., Ltd., EPX 4 0 6 1 and other rubber modified epoxy resins; Dicyclopentadiene phenol type epoxy resin made by Sanyo Kokusaku Parp Co., Ltd. and other grades; polysiloxane modified epoxy resin made by Asahi Kasei Kogyo Co., Ltd. X-1 3 5 9; Ε-caprolactone modified epoxy resins made by Diacell Chemical Industry Co., Ltd. Placell G — 40 2, G — 7 1 〇, etc .; etc. are equivalent to soluble epoxy resin in diluent. These epoxy resins can be used singly or in combination of two or more kinds, but it is particularly preferable that they are dispersed in a particulate form in the photosensitive prepolymer (A). Therefore, it is better to be solid or semi-solid at normal temperature, and it may also be one that does not dissolve the aforementioned photosensitive prepolymer (A) and the diluent (C) used during kneading, and / or It is also possible to have solubility in a range that does not adversely affect light sensitivity and developability. That is, it is preferably used in the form of a particulate epoxy resin which is hardly soluble in a diluent; or a combination of a poorly soluble epoxy resin and a soluble epoxy resin. At this time, the blending amount of the epoxy resin that is soluble in the diluent is preferably a proportion of less than 50 mol% of the epoxy equivalent of the all epoxy compound as the thermosetting component. If the compounding ratio of the epoxy resin which is soluble in the diluent is 50 mol% or more (the compounding ratio of the poorly soluble epoxy resin in the diluent is less than 50 mol%), then the coating of the obtained composition is applied. After the film is dried, the finger touch drying property and development life are reduced, so it is not good. Also, Yu Da (Please read the notes on the back before this page) 1

— — — — —-- Order · I--11 11-* 5 ^ I f This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -19- 494276 A7 B7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative V. Description of the invention (17) Quantities used in the case of soluble epoxy resin in thinner 'Because it is easy to increase the viscosity of the printed circuit board before coating, it is desirable to prepolymerize (A) is used as the main component of the main agent, and the thermosetting component (D) is used as the main component of the two-liquid type composition, and the two are mixed and used at the time of use. That is, the blending amount of the epoxy compound (D) as the thermosetting component is preferably 5 to 100 parts by weight relative to 100 parts by weight of the photosensitive prepolymer (A), and is more than It is preferable that it is 15 to 60 parts by weight. In the composition of the present invention, the epoxy resin may be used together with an epoxy curing accelerator or a catalyst. Examples of the epoxy hardening accelerator or catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2 = phenylimidazole, 4-phenylimidazole, 1- Imidazole derivatives such as cyanoethyl-2, 2-phenylimidazole, 1- (2-cyanoethyl) -2, 2-ethyl-1, 4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-1 (Dimethylamino) amines such as N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Compounds, hydrazine compounds such as osmium adipate, hydrazine sebacate, etc .; phosphorus compounds such as triphenylphosphine, and the like, or commercially available products, such as 2 MZ-A, 2MZ — 〇KK manufactured by Shikoku Chemical Co., Ltd., 2PZZ, 2P4BZZ, 2P4MZZ (all are trade names of imidazole-based compounds), U-CAT3503X, U-CAT3502X (all are trade names of block isocyanate compounds of dimethylamine) manufactured by Sanapro, DBU, DBN, U — CATSAl〇2, U-CAT5002 ((Please read the precautions on the back before ordering page II --------- line — 9) This paper size applies to China National Standard (CNS) A4 regulations (210 X 297 mm) -20- 494276 A7 ___ B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) are all bicyclic fluorene compounds and their salts), etc. In particular, they are not limited to In this case, if it is a hardening catalyst for epoxy resins, or a catalyst that promotes the reaction between epoxy groups and carboxyl groups, two or more kinds can be used alone or in combination. In addition, guanidine which can function as an adhesion promoter can also be used. Amine, ethidium guanamine, benzoguanamine, melamine, 2,4-diamino-6-methacrylofluorenyloxyethyl-S-trioxane, 2-vinyl-1,4-diamine —Sangen, 2-vinyl—4,6-diamino group S —trioxo-isocyanuric acid adduct, 2,4-diamino-6—methacryloyloxyethyl-S—Sangen -S-trioxine derivatives such as isocyanuric acid adducts, and it is preferable to use these compounds which can also be used as the function of the adhesion-imparting agent for the aforementioned hardening contact. The compounding amount of the hardening catalyst In order to suffice in a normal proportion, for example, it is desirable to use 0.1 to 20 parts by weight relative to 100 parts by weight of the aforementioned photosensitive prepolymer (A). The ratio is preferably 0.5 to 15.0 parts by weight. With the components as described above as the necessary solder resist ink composition of the present invention, if necessary, the circuit of the printed circuit board, that is, copper oxidation, is prevented. For the purpose, compounds such as adenosine, vinyl sangen, dicyandiamide, o-tolylguanide, melamine, etc. can be compounded. The compounding range of these compounds is relative to the aforementioned photosensitive prepolymer (A) 1 〇〇 重量 parts is preferably a proportion of 20 parts by weight or less. By adding these substances, the chemical resistance of the solder resist film formed can be improved. In addition, for the purpose of improving properties such as adhesion, hardness, and solder heat resistance, if necessary, barium carbonate, barium titanate, silica powder, amorphous silica, talc, clay, magnesium carbonate, and calcium carbonate can be blended. , Alumina, aluminum hydroxide, glass fiber, carbon fiber, mica powder and other commonly used inorganic fillers (please read the precautions on the back before I ___ page ϋ ϋ ϋ · ϋ 一 n 1: 0, 1 ϋ ϋ I 1 ϋ ^ 1 I line ----------------------- _ This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm)- 21 _ 494276 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (19) 'and its blending ratio is 100 parts by weight relative to the aforementioned photosensitive prepolymer (A). The proportion is preferably, and it is preferably a proportion of 5 to 200 parts by weight. Moreover, the composition of the present invention may be blended with phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and crystal violet as required. Well-known and commonly used coloring agents such as, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone monomethyl ether, tertiary butyl catechol, pyrogallol, phenol Commonly known and commonly used thermal polymerization inhibitors, asbestos, micronized silica, organic bentonite, montmorillonite, and other commonly used thickeners, polysiloxane-based, fluorine-based, and molecular-based defoamers and / or Additives, such as leveling agents, imidazole-based, thiazole-based, triazole-based, and silane coupling agents, which are well-known and commonly used adhesion-imparting agents. The solder-resistant ink composition having the above-mentioned composition can be adjusted to be suitable for coating as required. The viscosity of the cloth method is applied on the printed circuit board forming the circuit by a silk screen printing method, a curtain coating method, a spray coating method, a roll coating method, and the like, and is, for example, at about 60 to 100 ° C. If the organic solvent contained in the composition is volatilized and dried (false-dried) at a temperature, a coating film with no wrinkles with a long development life can be formed. Thereafter, according to the contact method (or non-contact method), The photoresist is exposed with selective active light, and the unexposed portion is developed with a dilute alkali aqueous solution (for example, 0.5 to 5% aqueous soda carbonate solution) to form a photoresist pattern, and, for example, at about 1 4 0 to Heat at 180 ° C It can form a solder-resistant film with excellent adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation, and electrical corrosion resistance. The dilute alkaline aqueous solution used for the above imaging can be used. Use potassium hydroxide and hydrogen (please read the precautions on the back first). This page size applies to China National Standard (CNS) A4 (210 X 297 mm) n H · 1 · 1 ^ OJ · ϋ 1 1 ϋ ϋ ϋ · ϋ ϋ 1 ϋ I ϋ ϋ 1 1 1 1 ϋ ^ 1 ^ 1 1 1 1 _1 _1 ϋ ^ 1 ^ 1 · -22- 494276 A7 B7 V. Description of the invention (20) Sodium oxide, carbonic acid Dilute alkaline aqueous solution of sodium, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. In addition, the irradiation light for photocuring the coating film is suitably a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a metal halide lamp. In addition, laser light and the like can also be used as active light for exposure. After the solder-resistant film is formed as described above (or before the solder-resistant film is formed), the head plating layer formed on the surface of the conductor pad is preferably an electroless Ni-Au layer with excellent wettability with the solder body. However, the present invention is not limited to this, and if it is a plating layer having good wettability with the solder body, it can be applied even for other plating. That is, in this specification, the electroless plating Ni-Au refers to the combination of the electroless plating Ni and the electroless plating Au. Hereinafter, the present invention will be described in detail by way of examples and comparative examples. However, the following examples are only for the purpose of illustrating the present invention and are not intended to limit the present invention. That is, the following "parts" and "%" are all based on weight unless otherwise specified. In the following examples, the photopolymerization initiator shown in Table 1 below was used. (Please read the precautions on the back before 1 I I -page) Order --------- line! Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-23- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 494276 A7B7 V. Description of the invention (21) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 1 Photopolymerization initiators used in the examples and comparative examples, molecular weights and melting points fc) A bis (cyclopentadienyl) -bis (2,6-difluoropyrrole-1-yl) titanium (IRUGACURE 784, Ciba Specialty Chemicals) 534.4 163 ~ 165 B 2-Benzyl-2-dimethylamino-1- (4-morpholinyl) -butanone-1 (IRUGACURE 369, manufactured by Ciba Specialty Chemicals) 366.5 110 ~ 114 C 2,4,6-trimethylbenzidine biphenylphosphine oxide (RUSIRIN TPO) 348 87 ~ 93 D 2-methyl small [47 (methylthio) phenyl] -2-morpholinylacetone -1 (IRUGACURE 907, manufactured by Ciba Specialty Chemicals) 279.4 70 to 75 E 2,2-dimethoxy-1,2-biphenylethane-1-one (IRUGACURE 651, manufactured by Ciba Specialty Chemicals) 256.3 64 ～ 67 (Please read the precautions on the back first and then page 1 | ^ 4)-Thread · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 24- 494276 A7 B7 V. Description of the Invention (22) Synthesis Example 1 (Synthesis of Photosensitive Prepolymer (A)): Epiclone N -6 9 5 (creation of cresol novolac epoxy resin) Epoxy equivalent 222 (20) manufactured by Industrial Co., Ltd. was placed in a four-necked flask equipped with a stirrer and a reflux cooler, and 206 parts of carbitol acetate was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated at 95 to 105 ° C, and 72 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. The obtained reaction product was cooled to 80 to 90 ° C, 91 · 2 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours, and then taken out after cooling. The photosensitive prepolymer having both an ethylenically unsaturated bond and a carboxyl group obtained in this way was a non-volatile component of 65%, and the acid value of the solid product was 87 · 8 mgKOH / g. Hereinafter, a solution of this reaction product is referred to as A lacquer. Examples 1 to 4 The ingredients shown in Table 2 were blended using the "A lacquer" obtained in the aforementioned Synthesis Example 1. The ingredients were kneaded with three roller mills to obtain a solder resist ink composition. '(Please read the precautions on the back before β this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 494276 Α7Β7 V. Description of the invention (23) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 Cooperating with the trade name or chemical name of the raw material _ 1 2 3 4 Photopolymerization initiator A IRUGACURE 784 16 2 B IRUGACURE 369 • 16 10 10 Polymer A lacquer 160 160 160 160 Diluent 1 Dipropylene glycol monomethyl ether 40 40 40 40 Hardened catalyst for epoxy resin dicyandiamine 0.5 0.5 0.5 0.5 Melamine 1 1 1 1 Color pigment phthalocyanine green 1 1 1 1 Tincture barium sulfate 80 80 80 80 Defoamer KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 1 1 1 Photopolymerizable monomer ~ dipentaerythritol hexaacrylate 10 10 10 15 Epoxy resin TEPIC ( (Made by Nissan Chemical Industry Co., Ltd.) 15 15 15 15 (Please read the precautions on the back first ϋ ϋ · I · 1 ϋ--οτ ϋ · ϋ I ϋ I ϋ ϋ I _ This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 mm) -26- 494276 A7B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (24) Using the A lacquer obtained in the aforementioned Synthesis Example 1, knead the compounding ingredients shown in Table 3 with three roller mills to obtain a solder resist ink composition Table 3 Compound name or chemical name of the blended raw material Comparative Example 1 2 3 Photopolymerization initiator C RUCILIN TPO 16 D IRUGACURE 907 16 • E IRUGACURE 651 mile 16 Photosensitive prepolymer A lacquer 160 160 160 Diluent dipropylene glycol monomer Dimethyl ether 40 40 40 Hardening catalyst for epoxy resin dicyandiamine 0.5 0.5 0.5 melamine 1 1 1 color pigment phthalocyanine green 1 1 1 tincture barium sulfate 80 80 80 defoamer KS-66 (Shin-Etsu Chemical Industrial Co., Ltd.) 1 1 1 Photopolymerizable monomer dipentaerythritol hexaacrylate 10 10 10 Epoxy resin TEPIC (manufactured by Nissan Chemical Industries, Ltd.) 15 15 15 (Please read the precautions on the back before mf

------ Order --------- Line J This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -27- 494276 A7 B7 V. Description of the invention (25) Performance evaluation: (1) The amount of smoke generated (please read the precautions on the back and then this page). The ink compositions obtained in the foregoing Examples 1 to 4 and Comparative Examples 1 to 3 were formed on a patterned copper foil substrate. It was fully coated by screen printing, and dried at 80 ° C for 20 minutes. Secondly, this substrate was resisted by a negative film, and exposed as a solder-resistant type, and developed with a spray pressure of 1.5 kg / c π 1 wt% Na 2 CO 3 aqueous solution to form a photoresist. Pattern. Thereafter, each substrate was heated in a closed furnace under a thermal curing condition of 150 ° C × 60 minutes, and the generated smoke components were captured. The amount of this smoke generated was that the captured smoke components were dissolved in DMF (N, N-dimethylformamide), and GP C (manufactured by JASCO Corporation: BIP-I, detector: UV, measurement wavelength) 28 nm), and evaluated based on the following criteria. 〇: There is almost no smoke component. (Triangle | delta): The smoke component was confirmed a little. X: There are many smoke components. XX: There are quite a few smoke components. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) Touch-dryness after pseudo-drying The ink compositions obtained in the foregoing Examples 1 to 4 and Comparative Examples 1 to 3 were formed on a patterned copper foil substrate It was fully coated by screen printing, and dried at 80 ° C for 20 minutes', and the touch-drying property of this coating film surface was evaluated. The determination criteria are as follows. 〇: All non-sticky paper sizes are in accordance with China National Standard (CNS) A4 (210 X 297 mm) -28- 494276 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (26) △ : Only a little sticky person X: Tacky person (3) Development property The ink compositions obtained in the foregoing Examples 1 to 4 and Comparative Examples 1 to 3 were formed on a patterned copper foil substrate with silk. Screen printing was fully coated and dried at 80 ° C for 30 minutes. This substrate was resisted with a negative film, exposed as a solder resist pattern, and developed with a spray pressure of 1.5 kg / crri of a 1 wt% Na 2 C03 aqueous solution to form a photoresist pattern. . This substrate was then heat-cured at 150 ° C for 40 minutes in a closed drying oven to produce a test substrate, and subjected to the following characteristic evaluation tests. (4) Resistance to electroless gold plating The test substrate prepared as described above is immersed in an acidic degreasing solution at 30 ° C (2 0 v ο 1% aqueous solution of Makudar Mid, Metex L-5 B in Japan). It was degreased for 3 minutes, followed by immersion in water for 3 minutes. Next, the test substrate was immersed in a 14 · 3 wt% persulfate aqueous solution at room temperature for 3 minutes 'for mild saturation', and then immersed in running water for 3 minutes. The test substrate was immersed in a 1% sulfuric acid aqueous solution at room temperature for 1 minute and then immersed in sulfur water for 30 seconds to 1 minute. Next, the test substrate was immersed in a catalyst liquid (Metal Plating Activator 3500-10% v 1% aqueous solution made by Meltex Co., Ltd.) at 30 ° C for 7 minutes, and then the catalyst was applied to the flowing water. Soak in water for 3 minutes. Catalyst substrate to be tested will be nickel-plated at 85 ° C (please read the precautions on the back before page I ___) tr --------- line 丨 i This paper size applies to China Standard (CNS) A4 specification (210 X 297 MM) -29- 7 (42 49 A7 _____ V. Description of the invention (27) Liquid (Meltex Co., Ltd., Melplate N i — 8 6 5M 2 0 v ο 1 % Electrolytic solution, P Η 4 · 6) for 20 minutes and electroless nickel plating. The test substrate was immersed in a 10 ν 0 1% sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds. ~ 1 minute. Next, the test substrate was immersed in a gold plating solution (manufactured by Meltex, Ourolectroles UP 15v〇1% and gold potassium cyanide 3vo 1% aqueous solution, p Η 6) at 95 ° C for 10 minutes. After electroless gold plating, immerse and wash in running water for 3 minutes, and immerse and wash in warm water at 60 ° C for 3 minutes. After sufficient water washing, spray and dry the water sufficiently to obtain the electroless gold-plated test substrate. After the test substrate was plated with gold, the presence or absence of peeling of the photoresist layer when peeled with a cellophane adhesive tape was evaluated. And the presence or absence of penetration of the plating solution (adhesion h. The judgment criteria are as follows. ○: No change was observed at all. △: The photoresist layer peeled slightly and the plating solution penetrated. X: Photoresist layer peeling (5) No electrolysis The plating property of N 1 -A u was obtained using a newly prepared plating bath, and electroless plating N i-A u was applied to each test substrate in the same manner as in (4) above, and the electroless plating N i -Au film was measured. Thickness and ease of plating evaluation are used as indicators of the wettability of the conductive pad and the head plating (and thus the wettability of the conductive pad and the solder body). The evaluation is based on the thickness of the plating film of the unformed solder substrate. The standard is based on the following judgments: This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back »» Page I Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

· -II ϋ ϋ ϋ I ii ^ li 11 · 1 · * ϋ 1 · 1 I 1 I ϋ i_i 1 i_i n ϋ ϋ in _ language R -30- 494276 A7 B7 V. Description of the invention (28) 〇: Good plating. △: The plating properties were slightly deteriorated. X: Poor plating properties. (6) Pollution of the plating bath Considering the test results of the amount of smoke generated in (1) above and the easy adhesion of the smoke to the substrate during heat curing, evaluate the effect of the pollution on the plating bath. The evaluation criteria are as follows. 〇: No pollution in the plating bath △: Possibility of contamination of the plating bath X: Possibility of contamination of the plating bath (7) Heat resistance of the solder flux After coating the rosin-based flux on the test substrate, it is set to 2 6 in advance. After being immersed in a solder bath at 0 ° C for 30 seconds, the flux was washed with trichloroethane, and the expansion (adhesion) of the photoresist film was evaluated visually. Peeling and discoloration. The evaluation criteria are as follows. _ 〇: No change is observed at all △: Only a little change X: Photoresist film swells and peels (8) Acid resistance The aforementioned test substrate is immersed in a 10 volt 〇1% sulfuric acid aqueous solution at normal temperature for 30 minutes, After washing and peeling test with cellophane adhesive tape (please read the precautions on the back before impinging this page) -Line · Printed by the Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies Chinese national standard (CNS) A4 Specifications (210 X 297 mm) -31-494276 A7 R7 V. Description of the invention (29) Examination of the peeling (adhesion) and discoloration of the photoresist film. The evaluation criteria are as follows: ○: No change was observed at all. △: Only a little change. X: Photoresist film peeled off. The results of the above tests are shown in Table 4. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 4 Example Comparative Example 1 2 3 4 1 2 3 Smoke generation amount 〇〇〇〇 △ X XX Dryness of finger touch after drying ◎ ◎ ◎ 〇〇〇Δ Imaging Properties ~ 〇 〇 〇 〇 00 non-electrolytic gold plating resistance 〇 〇 〇 000 pollution of the plating bath △ XX XX electroless Ni-Au plating properties 〇 00 △ XX solder heat resistance. As shown in the results shown in Table 4, the solder-resistant ink compositions of Examples 1 to 4 of the present invention have a small amount of smoke generation, and therefore are not harmful to the substrate. It will adhere to smoke, and the Ni-Au coating has good plating properties (adhesiveness). It is required to be dry and developable after touch-drying, and it is required for solder resistance @ W _ (Please read first Note on the back page) I .. Order --------- line 丨 i This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -32- 494276 A7 B7 V. DESCRIPTION OF THE INVENTION (30) Each characteristic such as heat resistance and acid resistance is excellent. In addition, for the test substrates of Examples 1 to 4, when electroless plating Ni-Au was applied and the peel test was performed with a cellophane adhesive tape after applying the solder, and no solder peeled, and The solder body has good adhesion to the conductor pad. On the other hand, in the comparative examples, particularly in the comparative examples 2 and 3, peeling of the solder body occurred, and the solder body was inferior in bonding properties to the conductor pad. That is, according to the solder-resistant ink composition of the present invention, it can be confirmed that the conductive pad having good wettability with the solder body, which can meet the originally required characteristics of the solder-resistant object such as heat resistance and adhesion of the solder, that is, with the solder Head pass plating such as N 1-Au plating with good wettability of the drug body forms good adhesion. Alas, as clarified by the results of Comparative Examples 1 to 3, and especially Comparative Example 3, it can be seen that the lower the melting point of the photopolymerization initiator, the more the amount of smoke generated, and the dryness of the fingers after drying is also reduced. As explained in the results of Example 4, if a photopolymerization initiator having a melting point of 100 ° C or more is used according to the present invention, the amount of the photopolymerizable monomer can be made even if the amount of the photopolymerization initiator is reduced. Increase and obtain a good photoresist coating film. Synthesis Example 2 In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, methyl methacrylate, ethyl methacrylate, and methacrylic acid were added at a molar ratio of 1: 1: 2 and added. Dipropylene glycol monoethyl ether as a solvent and azobisisobutyronitrile (AIBN) as a catalyst were stirred at 80 ° C for 4 hours under a nitrogen atmosphere to obtain a resin solution. This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before page I i

------ Order --------- Line J Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-33- 494276 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ) This resin solution is cooled, using methyl hydroquinone 'as a polymerization inhibitor, tetrabutyl bromide as a catalyst, and glycidyl methacrylate at 9 5 to 105 ° C for 16 hours. As a condition, an addition reaction is performed at 20 mol% with respect to the carboxyl group of the resin, and after cooling, it is taken out. The photosensitive prepolymer having both ethylenically unsaturated bonds and carboxyl groups obtained in this way is a non-volatile component of 6 5%, an acid value of a solid substance of 12 Omg KOH / g, and a Mw of about 20.0. 0 0. This resin solution is hereinafter referred to as Beta-lacquer. Synthesis Example 3 In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, methyl methacrylate and glycidyl methacrylate were added at a molar ratio of 4 ·· 6, and carbitol as a solvent was added. Alcohol acetate, AI ΒΝ as a catalyst, was stirred at 80 t for 4 hours under a nitrogen atmosphere to obtain a resin solution. This resin solution was cooled, using methylhydroquinone as a polymerization inhibitor, tetrabutyl bromide as a catalyst, and acrylic acid at a temperature of 95 to 105 ° C for 16 hours. The epoxy group of the resin undergoes an addition reaction at 100 mole%. The reaction product was cooled to 80 to 90 ° C, and reacted with tetrahydrophthalic anhydride for 8 hours. After cooling, the reaction product was taken out. The photosensitive prepolymer having an ethylenically unsaturated bond and a carboxyl group obtained in this way is a non-volatile component of 65%, an acid value of a solid substance of 100 mg KOH / g, and a Mw of about 15 ' 0 0 0. Hereinafter, this resin solution is referred to as C-varnish. (Please read the precautions on the back first, then page I · I J f, _ · ϋ 1 · ^ n βϋ ϋ 1 ϋ I MMmm I ammMm I ϋ «ϋ · ϋ ϋ ϋ 1 · ϋ n ϋ 11 words The dimensions are in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -34- 494276 A7 B7 V. Description of Invention (32) Synthesis Example 4 A four-necked flask equipped with a stirrer and a reflux cooler was charged with cresol Novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1045, softening point 92 ° C, epoxy equivalent = 220) 2200 parts (10 equivalents), 134 parts of dimethylolpropionic acid (1 Mo (Ear), acrylic 6 4 8 · 5 parts (9 moles), methyl hydroquinone 4. 6 parts, carbitol acetate 1 1 3 1 parts and solvent petrolatum 4 8 4. 9 parts, and at 9 0 The mixture was heated and stirred at ° C to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C and charged with 13.8 parts of triphenylphosphine, heated at 1000 ° C, and reacted for about 3 to 2 hours to obtain an acid. The reaction product with a valence of 0.5 to 1 ^ 〇11 / 2 (hydroxyl group: 12 equivalents). Secondly, 3 6 4 · -parts (2.4 moles) of tetrahydrophthalic anhydride and carbitol acetate were added thereto. 1 3 7 · 5 servings And solvent naphtha 58.8 parts, and heating at 95 ° C, reaction for about 6 hours, cooling, the acid value of the solid component is 40 mg KOH / g, the concentration of the solid component is 65% Unsaturated polycarboxylic acid resin. Hereinafter, this resin solution is referred to as D lacquer. Synthesis Example 5 A four-necked flask equipped with a stirrer and a reflux cooler was charged with a cresol novolac lacquer type epoxy resin. (Manufactured by Nippon Kayaku Co., Ltd., EOCN — 1045, softening point 92 ° C, epoxy equivalent = 220) 2200 parts (10 equivalents), 402 parts of dimethylolpropionic acid (3 moles), acrylic acid 5 0 4 · 4 copies (7 moles), methyl hydroquinone 4 · 8 copies, Carbene paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before ordering:- -Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-35- Outer 4276 A7 B7 V. Description of the invention (33) (Please read the precautions on the back before the page) Alcohol acetate 1 1 7 8 and solvent naphtha 5 5 parts of oil, heated and stirred at 90 ° C to dissolve the reaction mixture. Second, the reaction solution was cooled to 60 ° C, and charged Phenylphosphine 4.3 parts of 1, 1 billion heated at 0 ° C, the reaction for about 32 hours to obtain an acid value of square K〇H · 8 mg / g of reaction product (hydroxyl group: 16 equivalents). Next, add 402.5 parts of tetrahydrophthalic anhydride (2.665 moles), 133 parts of carbitol acetate and 57.3 parts of solvent naphtha, and heat at 9 5 ° C, the reaction is about 6 After cooling for hours, an unsaturated group-containing polycarboxylic acid resin (hydroxyl group: 1 3 · 35 equivalent) having an acid value of 3 · 6 mgKOH / g of a solid component was obtained. Next, 185.9 parts (1.2 mol) of ethyl methacrylate, 70 parts of carbitol acetate and 30 parts of solvent naphtha were added thereto, and heated at 50 ° C to react. After 10 hours, the infrared absorption spectrum was measured, and it was confirmed that there was no isocyanate group, so the reaction was completed. The acid value of the solid component was 40 mg KOH / g, and the concentration of the solid component was 6 5%. Acid urethane resin. Hereinafter, this resin solution is referred to as E-varnish. Examples 5 to 8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, using the B to E lacquers obtained in the foregoing Synthesis Examples 2 to 5, kneading the compounding ingredients shown in Table 5 with three roller mills to obtain solder-resistant inks Composition -36- $ Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 494276 A7B7 V. Description of invention (34) Printed by employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 Chemical name Example 5 6 7 8 Photopolymerization initiator A IRUGACURE 784 16 2 UV B IRUGACURE 369 _ 16 10 10 Photosensitive prepolymer B lacquer 160 C lacquer • 160 D lacquer • 160 lacquer E- Surface 160 Diluent Dipropylene glycol monomethyl ether 40 40 40 40 Hardening catalyst for epoxy resin dicyandiamine 0.5 0.5 0.5 0.5 Melamine 1 1 1 1 Coloring pigment ~ Phthalocyanine green 1 1 1 1 Filler barium sulfate 80 80 80 80 Defoamer KS-66 (made by Shin-Etsu Chemical Industry Co., Ltd.) 1 1 1 1 Photopolymerizable monomer dipentaerythritol hexaacrylate 10 10 10 15 Epoxy resin TEPIC (made by Nissan Chemical Industry Co., Ltd.) 15 15 15 15 (Please read the note on the back first Matters again Xia ___; line · This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -37- / i 2 94 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7 __5 Explanation of the invention (35) For each of the ink compositions obtained in the foregoing Examples 5 to 8, the amount of smoke generation was also evaluated, and the dryness, the developability, the electroless gold resistance, and the electroless N i- The plating properties of Au, the contamination of the plating bath, the heat resistance of the solder, and the acid resistance can be expected to be the same as the evaluation results of Examples 1 to 4. Effects of the Invention-As explained above, according to the present invention, , It is a solder-resistant ink composition that provides light-curing and thermal-curing properties without generating smoke during the heating process. As a result, the use of such a photo-curing and thermosetting solder-resistant ink composition can suppress heat. The occurrence of fumes in the light-hardened coating film of the solder-resistant composition during hardening can not only reduce the poor adhesion of the solder during the manufacture of the printed circuit board, but also achieve the effect of improving the working environment. Furthermore, the solder-resistant composition can be obtained through exposure. Light The coating film is free of transverse folds, and will not be closely combined with the photomask to improve workability. In addition, the solder heat resistance and the adhesion to the circuit board are required. Therefore, it is possible to manufacture a solder-resistant ink composition for a printed circuit board suitable for stable supply and formation of a conductive pad having a good adhesion to the lead of the wettability of the solder body. (Please read the precautions on the back before I-ϋ Page Order --------- Line — 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -38-

Claims (1)

494276 A8 B8 C8 D8 Announcement VI. Application for Patent Scope No. 89 1 08638 Patent Application Chinese Patent Application Amendment (please read the precautions on the back before filling this page) Revision in May 91 of the Republic of China1. A solder resistance An ink composition for forming a solder resist on a printed circuit board formed with a bottom plating layer formed on a surface of a conductor pad. The ink composition contains (A) in one molecule and has both a base and at least two ethylenic properties. Unsaturated bond, photosensitive prepolymer having a solid component acid value of 40 to 150ragKOH / g, (B) a photopolymerization initiator having a melting point of 100 ° C or higher, and (C) a diluent And (D) a thermosetting component having an epoxy compound having two or more epoxy groups in one molecule as a main component. 2. The composition according to item 1 in the scope of the patent application, wherein the photopolymerization initiator (B) is 2-benzyl-2-dimethylamino- (4-morpholinephenyl) -1 butane 1-one, and / or bis (β5-2,4 -cyclopentadiene-1-yl)-bis (2,6 -difluoro -3-(1Η-pyrrole -1 -yl) -phenyl) titanium . Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs3. The composition as described in item 1 of the scope of patent application, wherein the photosensitive prepolymer is at least one selected from (1) so that one molecule has more than two epoxy resins A resin obtained by performing an esterification reaction of a multifunctional epoxy compound (a) with an unsaturated monocarboxylic acid (b), and reacting the obtained esterified group with a saturated or unsaturated polybasic acid anhydride (c), 2) Let the copolymer of (fluorenyl) acrylic acid and other copolymerizable monomers (d) with ethylenically unsaturated bonds be partially compatible with (meth) acrylic acid. This paper applies Chinese National Standard (CNS) M specifications (210 X 297 mm) 494276 Printed by A8, B8, C8, D8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Resins obtained by reaction of glycidyl esters in patent applications. (3) Order glycidyl (meth) acrylate and other ethylenic compounds. A copolymer of an unsaturated bond copolymerizable monomer (d), a resin obtained by reacting with an unsaturated carboxylic acid (b), and reacting the hydroxyl group of the obtained reaction product with a saturated or unsaturated polybasic acid anhydride (c), (4 )make Polyfunctional epoxy compound (a) having two or more epoxy groups in one molecule, and unsaturated monocarboxylic acid (b), and one having at least two kinds of hydroxyl groups in one molecule and reacting with epoxy groups A reaction product (I) of a compound (e) of another reactive group, a resin obtained by reaction with a saturated or unsaturated polybasic acid anhydride (c), (5) an unsaturated polybasic acid anhydride such as maleic anhydride and styrene, etc. Copolymers of aromatic hydrocarbons having vinyl groups, resins obtained by reaction with hydroxyethyl (meth) acrylate, and (6) the reaction product (I) and the saturated or unsaturated polybasic acid anhydride (c) and Resin obtained by reacting an unsaturated monoisocyanate (f). 4. The composition according to any one of claims 1 to 3 in the scope of patent application, wherein the composition contains 1 to 30 parts by weight of the photosensitive prepolymer (A) in an amount of 100 parts by weight. Photopolymerization initiator (B). 5. The composition according to any one of claims 1 to 3 in the scope of patent application, wherein the diluent (C) is an organic solvent and contains 30 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A). ~ 300 parts by weight of diluent (C). 6. The composition as described in any of items 1 to 3 of the scope of the patent application applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the precautions on the back before filling this page) Order # 4. -2- 494276 A8 B8 C8 ____D8 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of the patent application, where the diluent (C) is a photopolymerizable monomer, relative to the photosensitive prepolymer (A) It is 100 parts by weight and contains a diluent (C) in a proportion of 40 parts by weight or less. 7. The composition as described in any one of items 1 to 3 of the scope of patent application, wherein the epoxy compound (D) is a poorly soluble epoxy resin in a diluent (c) used, or Mixture of poorly soluble epoxy resin and soluble epoxy resin in the diluent (C) used. 8. The composition according to any one of claims 1 to 3 in the scope of the patent application, wherein the composition contains 5 to 100 parts by weight relative to 100 parts by weight of the photosensitive prepolymer (A). This epoxy compound (D) ° 9 · The composition according to any one of claims 1 to 3 in the scope of patent application, which further contains a hardening accelerator for epoxy resin. 10. The composition according to any one of claims 1 to 3 of the scope of patent application, which further contains an inorganic filler. 1 1 The composition according to any one of claims 1 to 3, which further contains a coloring pigment. 1 2. The composition according to any one of claims 1 to 3 in the scope of patent application, which further contains an antifoaming agent or a leveling agent. This paper size applies Chinese National Standard (CNS) A4 specification (21〇 X 297 mm) 鬌 (Please read the precautions on the back before filling this page)-口 .1 · -3-