TW201015216A - Black solder resist composition and cured product thereof - Google Patents

Abstract

The present invention provides a black solder resist composition which can maintain light curing property at deep layers even for the case of deep black color, characterized by including: a resin (A) containing carboxyl; photo-polymerization initiator (B); diluent (C); polyfunctional epoxy compound (D), each molecule of which contains plural epoxy groups; and coloring agent (E), wherein the coloring agent is blacked by selecting from any combination of the following groups: yellow and purple coloring agents; yellow, blue and red coloring agents; green and purple coloring agents; green and red coloring agents.

Description

201015216 Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the formation of a permanent agent for use on a printed circuit board. More specifically, the present invention relates to a black solder mask and a cured product which are applicable to a high-density printed circuit board and which are darker in color to black. (10) Body image resolution [Prior technology] Φ In recent years, with the remarkable progress in the field of semiconductor technology, the era of ultra-LSI has rapidly promoted the shortening of electronic devices, shaping, thinning, and light weight. . In this regard, the printed circuit board is also highly densified and highly thinned, and further requires high precision and high performance. Corresponding to this demand, the solder mask of the outermost layer of the printed circuit board is used as a permanent mask. The resolution of the layer, the dimensional accuracy, the adhesion, the electrolessness, and the electrical properties are also improved. The high requirements have also created new requirements. For example, because it is difficult to recognize the contrast of the conductor patterns of various printed circuit boards, the color tone of the liquid light solder resist 1 (6) cuts the need for deep black (for example, reference to patents). Document 1). Further, in the past, a carbon black pigment was used as a black light solder resist (Patent Document 2). This black pigment shows the absorption wavelength from the ultraviolet field to the infrared field. Therefore, in order to improve the blackness, the black light anti-corrosion napkin of the black pigment content is improved, and the light is hardened, and the exposure light is absorbed by the black pigment, so that the photohardening cannot be sufficiently performed, and the exposure sensitivity obtained is The resolution is low. Therefore, it is difficult for the black light solder resist of the board to be applied to the recent high-density and high-thinness printed wiring, and it is difficult to obtain the resolution required for the high-density pattern. That is, increasing the amount of the carbon black pigment added so that the black color is deep will significantly lower the light hardenability in the deep portion. Therefore, if 201015216 wants to require photohardenability (resolution), there will be a problem that black must be lightened. [Patent Document 1] JP-A-2000-294131 [Patent Document 2] JP-A-2002-294131 SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides a black solder resist which is capable of deep photohardening even in black deep. Resist composition and hardened material thereof. ,··, the present invention is in the above problem, by mixing two or more kinds of black

Outside _ 峨 防 防 防 防 防 , , , , , , , , , , , , , , , , , 目 目 目 目 目 目 目 目 目 目 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ a composition comprising: a resin containing a slow base (A); a photopolymerization initiator (B); a diluent (C); a surface 峨 compound _ the agent (E) is selected from the group consisting of yellow color And blue colorant and red colorant, 怂Kg colorant, and green colorant and red colorant group. (2) A black solder resist composition characterized by a resin containing a carboxyl group (Α ';' photopolymerization initiator (Β); diluent (C); ¢)); 1 molecule having a plurality of epoxy groups of polyfunctional ring bombs and coloring agents), wherein the colorant (E) by containing a yellow colorant selected from the group consisting of: 201015216 1 part by weight and a purple colorant of 0.01 to 10 parts by weight, 1 part by weight of yellow colorant and 0.01 to 10 parts by weight of 'blue coloring 0_01 to 10 Red coloring agent for weight, 1 1 part by weight of green coloring agent and 紫色.〇1~1〇 weight part of purple coloring agent, 1 part by weight of green coloring agent and 〇.〇1~10 weight The red colorant of the measuring portion is blackened by any combination of the groups. (3) The black solder resist composition according to claim 1, wherein the combination of the colorant (E) is a combination of a purple colorant and a yellow colorant group & 盥 blue colorant. (4) The black solder resist composition according to claim 2, wherein the combination of the colorant (E) is a yellow colorant of the weight of the crucible and a weight of the crucible The combination of the purple colorant and the blue coloration combination of the weight of the 〇.〇1~1〇. (5) The black solder resist composition as described in claim 1 of the patent application, wherein

In the combination of the colorant (E), a green colorant is combined with a red colorant group & blood blue colorant. (6) The black solder resist composition according to claim 2, wherein the combination of the agent (E) is a weight of 1 part by weight of the green colorant and 〇〇1 2〇. The combination of the red color toner is combined with a blue colorant of 0.01 to 10 parts by weight. (7) The black solder resist composition according to any one of claims 1 to 6, wherein the hardened matter has an L* value of 33 or less, and the a* value and the b* value are 〇±3. Within the scope. (8) The black solder resist 5 201015216 resist composition according to any one of claims 1 to 7, wherein a black colorant is additionally added. (9) A cured product of a black solder resist composition comprising a colorant, characterized in that the colorant comprises a yellow colorant and a purple colorant, a yellow colorant and blue, a colorant and A red colorant, a green colorant and a purple colorant, and any combination of a green colorant and a red colorant. (10) A cured product of a black solder resist composition comprising a yellow colorant selected from the group consisting of 1 part by weight and 〇〇1~1〇 The purple coloring agent of the weight part '1 4 parts of the yellow coloring agent and the blue coloring agent of the weight part of the 〇〇1~1〇 and the red coloring agent of 0.01~10 parts by weight, the green coloring agent of the weight part of the 与1 and 0.01~ A combination of a 10-weight purple colorant, a green colorant of the weight portion, and a red colorant of 0.01 to 10 parts by weight. (11) The hardening of the black solder resist composition according to claim 9, wherein the coloring agent contained in the hardened material is a blue colorant and a purple colorant added with a blue colorant And formed. (12) The cured product of the black solder resist composition according to claim 10, wherein the coloring agent contained in the hardened material is one part by weight of the yellow colorant and 0.1 to 10 parts by weight. The purple colorant is formed by adding a 01 to 1 〇 weight coloring agent. (13) The cured product of the black solder resist composition according to claim 9, wherein the coloring agent contained in the hardened material is added to the green colorant and the red colorant by adding a blue colorant. form. ^ (14) The hardening of the black solder resist composition according to claim 10, wherein the coloring agent contained in the hardened material is a green agent of the weight of j and 0.1 to 10 parts by weight. The red colorant is formed by adding 01 to 1 weight: 'coloring agent. (15) The cured product of the black resist composition according to any one of the items 9 to 14, wherein the L* value is 33 or less, and the a* value is within the range of 〇±3. . The cured product of the black anti-Φ resist composition according to any one of claims 9 to 15, which contains a black colorant. (17) A cured product of a color solder resist composition according to any one of claims 9 to 16, which contains (H to 8 wt% of a coloring agent. In the present specification, The description of the scope of application for patents, red, yellow, green, blue, purple is as defined below. - The so-called red means RP red purple ~ R red as shown in the first figure 10P ~ 10R. The so-called yellow means the first YR yellow red ~ γ yellow shown in Fig. 10R~10Y. The so-called green means GY yellow green ~ 0 ~ ΒΘ green green as shown in Fig. 0Y40BG of the first figure. The so-called blue means 10BG as shown in the first figure. ~10PB shows B blue ~ PB light purple. "" The so-called purple refers to the ρ purple as shown in the first figure 10ΡΒ~10Ρ. (Effect of the invention) According to the present invention, 'by combining two or two The solder resist composition of the colorant other than the above black colorant is blackened, and the absorption amount of the exposure light from photohardening is small as compared with the case where only the black colorant is used. Therefore, even if the black color is increased To increase the content of the colorant, the light hardening can still fully enter the 'sensitivity and solution The image quality can be effectively applied to a printed circuit board having a high density and a high thinness by using only a black coloring agent. 201015216 [Embodiment] Hereinafter, an embodiment of the present invention will be described in detail. The black solder resist composition of the present invention comprises: (A) a mercapto group-containing resin, (B) a photopolymerization initiator, and (c) a diluent 'pμ molecule having a plurality of epoxy groups in a polyfunctional ring Oxygen compound and two or more kinds of coloring agents (Ε) mixed with blackening. Hereinafter, individual components will be described. (Α) Resin containing a slow base

(1) A carboxylic acid-containing copolymerized resin obtained by copolymerizing an unsaturated citric acid such as methacrylic acid with a compound of one or more kinds of unsaturated double bonds. (2) unsaturated tetamine such as methacrylic acid and one or more compound copolymers having an unsaturated double bond, by glycidyl methacrylate ( Glycidyl methacrylate, GMA) or a compound having an epoxy group and an unsaturated double-stranded chain such as 3,4-epoxycyclohexyl methyl methacrylate or by methyl Methacrylie chloride or the like, a carboxylic acid-containing photosensitive resin obtained by adding a ethylenically unsaturated group as a pedant group. (3) having epoxy groups and unsaturated and double-stranded groups such as glycidyl methacrylate (GMA) or 3,4-epoxycyclohexyl methyl methacrylate In the copolymer of the compound and one or more compounds having an unsaturated double bond, an unsaturated carboxylic acid such as methacrylic acid is reacted to form a secondary hydrogen group and a plurality of A photosensitive resin containing a carboxylic acid obtained by reacting an anhydrous chloroformate. (4) In an interpolymer of an anhydrous acid having an unsaturated double-stranded chain such as anhydrous maleic acid and a compound having an unsaturated double-stranded complex, 201015216, 'making 2-ethyl acetoacetate phyiJroxyethyl A carboxylic acid-containing photosensitive resin obtained by reacting a hydroxyl group in a methacrylate or the like with a compound having an unsaturated double-chain. (5) A photosensitive resin containing a carboxylic acid obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid to react a generated hydroxyl group with a saturated or unsaturated polychlorinated acid anhydride.

(6) After reacting a saturated or unsaturated polybasic acid anhydrate in a polymer containing a hydroxyl group such as a polyvinyl alcohol inducer, the resulting carboxylic acid has an epoxy group and an unsaturated double in one molecule. A photosensitive resin containing a hydroxyl group and a carboxylic acid obtained by reacting a compound of a chain. (7) a compound having a reactive group other than an alcoholic hydroxyl group which reacts with a polyfunctional epoxy compound, an unsaturated monobasic acid, an alcoholic hydroxyl group having at least one molecule, or an epoxy group, with or without a saturated or not A photosensitive resin containing a carboxylic acid obtained by reacting a saturated polychlorinated acid with an anhydride.

(8) reacting a polyfunctional epoxidized compound having a plurality of oxetane rings in one molecule with an unsaturated monocarboxylic acid to give a first-order hydroxyl group in the obtained denatured propylene oxide The photoreceptor resin I (9) obtained by the reaction of a saturated or unsaturated polychlorinated acid anhydride is obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid to form an anhydrous anhydride with a polychlorinated acid. A carboxylic acid-containing photosensitive resin obtained by reacting a carboxylic acid-containing resin obtained by the reaction with a compound having one oxirane and one or more ethylenically unsaturated groups in the molecule. Although the above compounds are exemplified, they are not intended to be limiting. In the above-described examples, it is preferable to use the photosensitive resin containing the carboxylic acid in the above (2), (5), (7), and (9), and in particular, the photosensitive resin containing the carboxylic acid in the above (5) is in the light. It is preferable in terms of hardenability and hard coating film properties. Further, in the present specification, methacrylate is an acrylic type 201015216 (acrylate, (metha)acryiate;) and a mixture thereof and the like. 8. The carboxylic acid-containing resin (A) as described above has a plurality of free carboxyl groups in the side chain of the backbone polymer, and can be visualized by a diluted alkaline aqueous solution. The acid value of the above carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mg KOH/g, more preferably in the range of 45 to 120 mg KOH/g. If the acid value of the resin containing the carboxy group (A) is less than 4 〇 mg KOH/g 'basic imaging, it will be difficult. On the other hand, if it exceeds 2 〇〇 mg KOH/g, the developing solution will be dissolved in the exposed portion, and the line will be too fine. Depending on the case, the exposed portion and the unexposed portion cannot be distinguished, and all are dissolved in the developing solution. It is difficult to delineate and depict a normal resist pattern (resist pattern), so it is not good. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin bone path, and is generally 2, _ 15 15 Å, _ is preferably in the range of 5 〇〇〇 to 1 〇〇〇〇〇. Better. If the weight average molecular amount of the carboxyl group-containing resin (A) is less than 2,000', the tack-free performance will be deteriorated, and the moisture resistance of the coating film after exposure will be deteriorated, resulting in a decrease in film formation during development. , the resolution is greatly degraded. On the other hand, when the weight average molecular weight of the resin (A) having a carboxyl group exceeds _150, the surface will be markedly deteriorated in development and the storage stability may be deteriorated. The mixing ratio of the resin (A) containing the retarding group is preferably from 2 to 6 % by weight based on the total composition, more preferably from 20 to 50% by weight. If the mixing ratio of the carboxyl group-containing resin (A) is less than the above range, the coating film strength will be lowered, which is not preferable. On the other hand, when the mixing ratio of the resin (A) containing a carboxyl group is more than the above range, problems such as an increase in viscosity and a decrease in coatability are also undesirable. (B) Photopolymerization initiator As the photopolymerization initiator (B), for example, acetophenone, 2,2-dimethoxy-2-phenylethylbenzene (2,2-dimethoxy) -2-phenylacetophenone), 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, Chlorophene _ 201015216 (dichloroacetophenone), trichloro acetophenone, p-tert-butyl trichloroacetophenone, 1-cyclohexyl phenyl ketone (1) -hydroxycyclohexyl phenyl ketone), 2-mercapto-l-[4-(methylthio)phenyl]-2-hydrazino-propanone (2-methyl-1 - [4-(methylthio)phenyl]-2 -morpholino-propan-1 -one), 2-phenylmercapto-2-dimethylamino-1-(4-indolylphenyl)-butanone (2-benzyl-2-dimethylamino-1 - ( 4-morpholinophenyl)-butanone-1), acetophenone such as N, N-dimethylaminoacetophenone; benzophenone, methyl diphenyl Methyl benzophenone, 2-chlorobenzophenone, 4,4 '4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzopheone, 4,4-bisdiethylamine Diphenyls such as 4,4-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide A class; benzyl, benzoyl, benzoin methyl _ ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoin ethers; acetophenone dimethyl ketal; benzyl dimethyl ketal and other condensate; thioxanthone, 2-xanthone (2 -chlorothioxanthone), 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc.; 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthene (1-c) Hloroanthraquinone), 2-amino anthraquinone, 2,3-di-phenyl (2,3-(^1161154〇111; 1^^11111〇116), etc. Organic peroxy compound such as benzoyl peroxide or cumene peroxide; 2,4,5-triarylimidazole dimer (2,4,5-triarylimidazole 11 201015216 dimer), 2 - Mercaptan benzoate (2-mercaptobenzoxazole), 2-mercaptobenzothiazole and other thiol compounds; 2,4,6-para-5-triazine (2,4,6- Tris-s-triazine), 2,2,2-tribromoethanol (2,2,2-tribromoetiianol), bis-tribromomethyl phenyl sulfone, etc.; 2,4,6- Trisylphenylbenzoyldiphenylphosphine oxide (2,4,6-trimethylbenzoyldiphenylphosphine oxide). These compounds may be used singly or in combination of two or more. Further, the above photopolymerization initiator (B) may also be neutralized with N,N-dimethylamino benzoic ethyl ester and N,N-didecylamine Φ group. N, N-dimethylamino benzoic isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. Tertiary amines; bis(??5-pentadienyl)-bis(2,6-difluoro-3-(111-fluoren-1-ylphenyl)titanium (bis( η 5-cyclopentadienyl)-bis (2,6-difluoro-3-( 1 H-pyrro-1 -yl) phenyl) titanium), etc. Titanocene; 2-(B-oxy-imine sulfhydryl) sigh 11 tons-9_ Ketone (2-(acetyl oxyimino methyl)thioxanthen -9-one); 1,2-octanedione (l,2-octandione), 1-[4-(phenylthio)-2-(0-benzyl) Will]] 1-[4-(phenylthio)-2-(0-benzoyloxime)] ethanone), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-咔3 Iazozo]-1-(0-acetamidine) (l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-l-(〇-acetyl〇xime)) One type or two or more types of photosensitizers such as esters are used in combination. In the combination of the agents (B), 2-methyl-1-[4-(methylthiol)phenyl]-2-morphin-propan-1-pyrene (2_methyl-l_[4-(methylthi〇) phenyl] -2-morpholino-propan-l-one) (for example, IRGACURE-907 manufactured by Ciba Specialty Chemicals, IRGACURE is a registered trademark), 2-chlorothioxanthone (for example, manufactured by Nippon Kayaku Co., Ltd.) KAYACURE-CTX, KAYACURE is a registered trademark) or 2,4-diethylthioxanthone (for example, KAYACURE-DETX made by Sakamoto Chemical Co., Ltd.), 2-isopropyl acrylate A combination of 2-isopropylthioxanthone, 4-phenylmercapto-4'-methyldiphenylsulfide 12 201015216 (4-benzoyl-4'-methyldiphenylsulfide) or the like is preferred. Further, the range of the use amount of the photopolymerization initiator (B) is preferably 5 to 30 parts by weight, and 5 to 25 parts by weight, based on 100 parts by weight of the base-based photosensitive resin (A). For better. If the mixing ratio of the photopolymerization initiator (B) is smaller than the above range, the photocurability of the composition obtained will be deteriorated. On the other hand, when the mixing ratio of the photopolymerization initiator (B) is more than the above range, the properties of the obtained cured coating film are deteriorated, and the storage stability of the composition is deteriorated, which is not preferable. (C) Diluent # As the diluent (C) ', an organic solvent and/or a photopolymerizable monomer can be used. Examples of the organic solvent used as the diluent (C) include ketones such as methyl ethyl ketone and cyclohexanone; and aromatic hydrocarbons such as toluene, Xylene, and tetramethylbenzene. Class; ceUos〇lve, methyl cellolve, butyl cellsolve, carbitol, methylcarbitol, butyl Butyicarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. 'Acetyl acetate, vinegar acetate, cellsolve acetate, butyl cellolve acetate, carbitol acetate, butyl glycol vinegar acetate (butyl carbitol acetate), acetates such as dipropylene glycol monomethylethei acetate; alcohols such as ethanol, propanol, ethylene glycoxime, and propylene glycol Octane, decane Aliphatic hydrocarbons thereof; petroleum ether, petroleum gas oil (Naphtha), add water, petroleum gas oil, gas oil solvent (s〇lvent Naphtha) and other petroleum-based solvents and the like. These organic solvents may be used singly or in combination of plural kinds. The purpose of using the organic solvent is to dissolve the above-mentioned carboxyl group-containing resin (A), dilute it as a liquid coating, and then semi-dry it to thereby form a film to be exposed to contact. 13 201015216 The amount of organic solvent used is not particularly limited and can be appropriately set according to the coating method selected. On the other hand, examples of the photopolymerizable monomer used as the diluent (c) include 2-hydroxyethyl methacrylate and 2-carboxypropyl propionate. 2-hydroxypropyl methacrylate), N-vinylpyrrolidone, acryloyl morpholine, meth〇xy tetraethylene glycol methacrylate, methoxy Methoxy polyethylene g yl methacrylate, polyethylene gylcol methacrylate, N,N-dimethyl decyl decylamine (N, N- Dimethyl methacrylamide), N-methylol methacrylamide, N,N-dimethyl aminopropyl methacrylamide, N,N- N,N-dimethyl aminoethyl methacrylate, N,N-dimethyl aminopropyl methacrylate, melamine acrylate (N, N-dimethyl aminopropyl methacrylate) Melamin methacrylate), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate Tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, phenoxyethyl methacrylate, tetrahydroftirfliiyl acrylate ), cyclohexyl methcarylate, glycerin diglycidyl ether dimethacrylate, glycerin triglycidyl ether trimechacrylate, propylene Isobomyl acrylate, cyclopentadiene mono or dimethacrylate, hexanediol, trimethylolpropane, isopentenol 201015216 (pentaerythritol), ditrihydroxymethylpropane (ditrimethyl Lpr〇pane), dipentaerylthritol, tm_hydroxyethyl iS0Cyanurate, polyvalent alcohols such as polyvalent acrylic acid or more, alcoholic ethylene oxide or Polyvalent oxime of propylene oxide addenda, polyesters of mono, bis, gin or above polyhydric acid and hydroxyalkyl hydrazine acrylate. These photopolymerizable monomers may be used singly or in combination of plural kinds. The purpose of the above photopolymerizable monomer is to transfer the aforementioned neodymium-containing tree sap (A) to a state in which it is easy to apply. , giving it photopolymerization. Regarding the appropriate amount of the photopolymerizable monomer, the amount of the resin containing the money base ❹ (4) is preferably in the range of 5 to 40 parts by weight in terms of 100 parts by weight. When the amount of the photopolymerizable monomer is less than that of the above-mentioned yarn, the effect of imparting light hardening will be insufficient, and if the above-mentioned fineness is exceeded, the dryness of the coating film will be lowered, which is not preferable. (〇) Polyfunctional Oxide Compound The black solder resist composition of the present invention has a plurality of ring-shaped polyfunctional rings in a molecule of a thermosetting component in addition to the above-mentioned respective components. The oxygen compound (D) can be applied to the formation of various resin insulating layers, anti-etching agents or marking inks, and is also suitable for the formation of solder resists for printed circuit boards. Examples of the polyfunctional epoxy compound (D) include EBPS-20G manufactured by Nippon Kayaku Co., Ltd., EPX_3G manufactured by Asahi Kasei Co., Ltd., and EPICLON EXA-l5l4 manufactured by Dainippon Ink Co., Ltd. (EPICLON is registered Bisphenol s type epoxy resin such as trademark); diglycidylphthalate such as BLEMER DGT (registered trademark) manufactured by Nippon Oil Co., Ltd.; Nissan Chemical Co., Ltd.

(share) system TEPIC (registered trademark), CIBA · SPECIALTY · CHEMICALS

Company ^^RADITE PT810 (ARADITE is a registered trademark) and other elements of the ring type of oxygen resin, oily SHELL EPOXY (shares) γ χ _4 〇〇〇, etc. - 曱 ( (bixylenol) type epoxy resin, oiled SHEIX YL- 6056 and other biphenol type epoxy resin, Dongdu Chemical Co., Ltd. ZX-1063 4 tetraglycidyl acetonitrile xylene bismuth bromide tetragiycidyiXyien〇i 15 201015216 ethane) resin and other epoxy resin which is difficult to dissolve in the diluent; Oiled SHELL EPOXY Co., Ltd. EPICOTE-1009, -1031 (EPICOTE is a registered trademark), Otsuka Ink Industrial Co., Ltd. EPICLON-3050, N-7050, N-9050, Asahi Kasei Industrial Co., Ltd. AER- 664, AER-667, AER-669, Dongdu Chemical Co., Ltd. YD-012, YD-014, YD-017, YD-020, YD-002, CEBA · SPECIALTY · CHEMICALS company XAC-5005, GT-7004 , 6484T, 6099, DER-462U, DER-673MF made by DOW CHEMICAL, bisphenol a type epoxy resin such as EP_54〇〇, Ep_59〇〇 made by Asahi Chemical Industry Co., Ltd.; ST-2004 made by Dongdu Chemical Co., Ltd. ST-2007 and other water-doped bisphenol A ❹ type epoxy resin; Dongdu Chemical Co., Ltd. YDF-2004, YDF-2007, Xinyi Iron Chemical Co., Ltd. GK-5079L and other bisphenol F Epoxy resin; Sakamoto Pharmaceutical Industry Co., Ltd. SR-BBS, SR-TBA-400, Asahi Chemical Industry Co., Ltd. EP-62, EP-66, Asahi Chemical Industry Co., Ltd. AER-755, AER-765 , Dongdu Huacheng (share) system YDB-600, YDB-715 and other evolution of bisphenol A type epoxy resin; 曰本化药(股) made EPPN-201, EOCN-103, EOCN-1020, EOCN-1025, BREN, Asahi Kasei Industrial Co., Ltd. ECN-278, ECN-292, ECN-299, CIBA · SPECIALTY · CHEMICALS ECN-1273, ECN-1299, Dongdu Chemical Co., Ltd. YDCN-220L, YDCN-220HH, YDCN-702 , YDCN-704, YDPN-601, YDPN-602, Dainippon Ink Chemical Industry Co., Ltd. 'Formed EPICLON-673, N-680, N-695, N-770, N-775 and other phenolic (nov〇lac) type Epoxy resin; Asahi Kasei Industrial Co., Ltd. EPX-8001, EPX-8002, EPPX-8060, EPPX-8061 'Essence of Ink Chemical Industry Co., Ltd. EPICLON-880 and other bisphenol A phenolic epoxy resin; Asahi Electrochemical industry (share) EPX-49-60, EPX-49-30 and other chelate type epoxy resin; Dongdu Huacheng (share) YDG-414 and other glyoxal type epoxy resin; Dongdu Turn into Λ^ΥΗ-14〇2,8Τ-11〇ΑΚ8ΗΕΙΧΕ ΡΟΧΥ(^^γι^931, YL-933 and other amine-containing epoxy resins; EPICLONTSR-60 Buxu Electrochemical Industry Co., Ltd. manufactured by Dainippon Ink Chemical Industry Co., Ltd., ΗΡΧ-84-2, ΕΡΧ-4061, etc. Denatured epoxy resin; dicyclopentadienephenolic epoxy resin such as DCE-400 manufactured by Shanyang Guoce PULP Co., Ltd.; Xudian Chemicals 16 201015216 X1359 and other cerium oxide denatured epoxy resin Resin; industry (stock) system PLACCEL G-402, G-71 〇箄ep meat ^ EL chemical transformation? Oxygen _ Ke dissolve __ towel alone or a combination of multiple systems, the towel peak dissolved in thinner Ίίίί! 1 lion, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The range of 〇~7〇 weight is better than the weight of 15~50.

(E) The colorant comprises a combination of a yellow colorant and a purple colorant, a yellow colorant and a blue colorant and a red colorant, a green colorant and a red colorant, or a yellow colorant and a purple color. A colorant and a blue colorant, or a combination of a 'color killing colorant' and a red colorant and a blue colorant. The coloring agents will be described below. (Green colorant) As a green coloring agent, 'a compound of phthalocyanines, 蒽 & b (anthraquinone) can be used. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent can be used. Green 5, Solvent Green 20, Solvent Green 28, etc. In addition to the above compounds, a benzene compound which is metal-substituted or metal-free may also be used. (Red colorant) As the red colorant, a monoazo, a diazo, an Azo lake, a benzimidazolone, or a second can be used. Perylene, DPP (diketopyrrolopyrrole) 'condensed azo, anthraquinone, quinacridone, etc., specifically, as exemplified below Color index number. Monoazo system: Pigment Red 1,2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21,22, 23, 31,32, 112, 114, 146, 147 , 151,170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, C. LPigment Orange 17 201015216 38; bisazo system: Pigment Red 37, 38, 41; Single azo precipitation color system: Pigment Red 48:1,48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68; benzoquinone σ sitting system: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208, CIPigment Orange 36 5 CIPigment Orange 64 ; phthalocyanine benzene series: Solvent Red 135, Solvent Red 179, Pigment φ Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224; DPP series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272, CI Pigment Orange 71, CI Pigment Orange 73; condensed gas system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Re d 220, Pigment Red 221, Pigment Red 242 » C.I. Pigment Brown 23 ; Brewing Department: Pigment Red 168, Pigment Red 177, Pigment Red ’ 216, Solvent Red 149, Solvent Red 150, Solvent Red 52,

Solvent Red 207; 啥°丫 ketones: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209. Pigment Violet 19 ; CI Pigment Orange 5( β -Naphthol)»CI Pigment Orange 34 ( Diaryl), CI Pigment Orange 13 (diaryl), CI Pigment Orange 61 (iso, 嗓琳_isoindolinone), CI Pigment Orange 43 (perylene); Purple coloring agent) As a purple coloring agent, specifically, for example, Pigment Violet 19, 23, 29, 18 201015216 32, 36, 38, 42; Solvent Violet 13, 36; CIPigment brown 25; CIPigment black 1, CI Pigment black 7, Pigment Violet 37 (dioxazine) and the like. (Yellow Colorant) As the yellow colorant, monoazo, diazo, condensed azo, benzimiazolone, and iso-zero can be used. Specific examples of the compound such as isoindolinone and anthraquinone include the following coloring agents. Single-event atmosphere: Pigment Yellow 1,2, 3, 4, 5, 6, 9,10,12, 61,62, φ 62:1,65, 73, 74, 75, 97, 100, 104, 105,111, 116, 167, 168, 169, 182, 183; bisazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198; condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180; benzoquinone 0 ketone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181; ° 嗓 嗓 : :: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185; Brewing System: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, CI Pigment Orange 13, CI Pigment Orange 61; (blue colorant) As a blue colorant, phthalocyanines can be used. , Anthraquinone ° oxazine (dioxazine) compound are classified as the pigment (Pigment), dyes (Solvent) were, as specifically include the following with color index (color index) number indicated. 201015216 Pigment: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2'Pigment Blue 15:3' Pigment Blue 15:4'Pigment Blue 15:6 ' Pigment Blue 16, Pigment Blue 60 5 Pigment Violet 23 ( Dyestuffs: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83 'Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70; and so on.

In addition to the above compounds, a benzene compound which has a metal substitution or a metal-free substitution can also be used. The appropriate combination of the blackening of the coloring agent and the mixing ratio thereof are as follows (in addition, the "part" represents the weight portion). (1) The combination of yellow and purple coloring agents, for one yellow Mix 〇.〇1~10 parts of purple, which is better to mix 01~5 parts; (2) Combination of yellow and blue and red coloring agents, for one part of yellow, mix 0.01~10 parts of blue Color 'is better to mix 〇 1~5 parts, mix 〇·〇1~10 parts of red, which is better to mix 01~5 parts; (3) combination of green and purple coloring agents, for 1 The green part of the department, mixed with 〇·01~10 parts of purple' which is mixed with 0.1~5 parts; the combination of mouth green and red coloring agent, for the green part of the part, mix 0·01~10 The red color is preferably 0.1 to 5 in combination; (5) the combination of yellow and purple and blue coloring agents. For the 'purple purple', the mixed color 'α〇1~10 parts of blue, Among them, 0.1 to 5 is preferred; (=) green and red and blue coloring agent combination is mixed _~1G part of red 'where to mix J ' 〇·ϋ~10 parts of blue, of which 0.1 to 5 are better 0 'cai' than mouth-on age _ 'even if not mixed /, blackened' and can obtain excellent resolution. Although the mixing amount of the coloring agents is not particularly limited, in addition to the organic solvent, all the constituent materials of the anti-hybrid composition of 20 201015216, the residual coloring agent in the solder resist layer is 0.1 to 8 wt%, Preferably, it is 2 to 5 wt%. (F) Black colorant 'The present invention may be additionally mixed with a black colorant (]?) as a black colorant, and suitable pigments may be, for example, cj pigment Black 6, 7, Carbon black pigments as shown in 9 and 18; graphite pigments shown by CI pigme Black 8, 10, etc.; c. Lpigment Blackll, 12 and 27, iron oxide pigments shown by Pigment Brown 35, for example Toda's industry (shares) 4 KN-370 iron oxide, Mitsubishi MATERIAL (stock) 13M titanium special Ctltamum black) 'C·1· Pigment black 20 and other enamel pigments; CX Pigment black 13, 25 and 29, etc. Oxidation-based pigments ^ q Pigment black 15 and 28, etc. CI pigment black 14 and 26, etc., lanthanide pigments; cI Pigment black 23 and the like, yttrium oxide pigments; CI Pigment black 30 and the like, shown as oxide pigments; CI Pigment black 31, 32 The aniline pigment shown in 7 Black 1 and the molybdenum sulfide or strontium sulfide. These materials can be used singly or in combination as appropriate. Among them, carbon black is particularly good, for example, carbon black M-4〇, M_45, M_5〇, MA-8, MA-ioo made by San's Chemical Co., Ltd., and 'perylene pigments in _ organic pigments It can effectively reduce halogenation. If the amount of the black colorant is too large, the object of the present invention cannot be achieved. Therefore, the total amount of the coloring agent selected from the group consisting of green, red, purple, yellow, and blue coloring agents is 50 parts by weight or less, and preferably 30 parts by weight or less. In the present invention, in relation to the black hue of the black solder resist ink, the L* value of the cured product obtained by the color difference meter is 33 or less, and the a* value and the b* value are all within the range of 〇±3. It is better. Further, in order to solve the above problem, the dry coating film (film thickness 25/zm) of the black solder resist ink is preferably 0.5 or more and 1.2 or less at a wavelength of 410 nm. The L* value and absorbance described herein are measured by the method described in the performance evaluation section of the examples to be described later. Therefore, the mixing ratio of the above-mentioned coloring agent or the mixing ratio of the components (Α) to (Ε) and any other components described later can be appropriately adjusted in consideration of the L* value or the absorbance. 21 201015216 (Other added components) In the present invention, in order to further improve characteristics such as adhesion, chemical resistance, and heat resistance, a curing catalyst can be further used in combination. As such a hardened coal, it can be exemplified by πm imidazole, 2-methyimidazole, 2-ethylimidazole, 2-ethyl-mercaptoimidazole ( 2-ethyl-4-methylimidazole), 2-phenylimidazole, 4-Phenylimidazole, 1-cyanoethy Uphenylimidazole, 1 -Isoimide inducer such as -(2-cyanoethyl)-2-ethyl-4-methylimidazole); dicyandiamide, benzoquinone Benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine (4-dimethylamino)-]Si, N_dimethylbenzylamine, 4-decyloxy-N,N-di Amine compound such as 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine; A compound such as adipose acid hydrazide or sebacic acid hydrazide; a phosphine compound such as triphenylphosphine; and a commercially available example, for example, the Shikoku Chemical Industry Co., Ltd. 2MZ made by the company -A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all of which are trade names of imidazole compounds); U-CAT3503N and U-CAT3502T manufactured by San-Apro Co., Ltd. (all of which are trade names of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (all of the above, a ring vein compound and its salt). In particular, it is not limited to such a compound, and it is also possible to use a thermosetting catalyst of an epoxy resin or an oxetane compound, either alone or in combination, or to promote an epoxy group and/or an oxypropylene group. Reactant with carboxyl groups. Further, it is also used as an adhesion imparting agent, guanamine, acetoguanamine, benzoguanamine, melamin, 2,4-diamino-6-fluorenyl. 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-ethylglycosyl-2,4-diamino-S-triazine (2-vinyl-) 2,4-diamino-S-triazine), 2-Ethyl-2,4-isodiamino-S-trisyl-cyanate addenda (2-vinyl-2,4-diamino-S -triazine · isocyanuric acid additives, 22 201015216 2,4-diamino-6-▼-based acryloxyethyl _s_triazine • cyanuric acid addenda (2,4-diamino-6-methacryloyl An S-triazine inducer such as xyxy-S-triazine, isocyanuric acid or the like, wherein a compound which acts as a tackifier as well as a heat-hardening catalyst is preferably used in combination. In the present invention, the amount of the above-mentioned curing catalyst may be in a usual ratio. In the first aspect, the black solder resist composition of the present invention can further improve the adhesion of the cured product, the mechanical strength, the coefficient of linear expansion, and the like, and the inorganic filler can be mixed. For example, barium sulfate, barium titanate, oxidized hair powder, micronized oxidized oxide, amorphous silica, talc, clay, magnesium carbonate, carbonated dance, alumina, and hydroxide can be used. A well-known inorganic filler such as aluminum or mica powder. The black solder resist composition of the present invention can further mix hydroquinone, hydr〇quin〇ne monomethylether, t-butyl phthalate (t) -butylcatechol), pyroallol, phenothiazine, and other known conventional thermal polymerization inhibitors, such as fine powdered sulphur dioxide, organic bentonite, montmorillonite (montm〇riU〇nite), etc. A well-known tackifier; a silicin, a fluorine-based, a polymer-based defoamer and/or a leveling agent; a sodium-salt, a thiazole, a triazine An additive such as a triazine or the like which is known to be used in the past. (Manufacturing method and use of the black solder resist composition) The black solder resist composition of the present invention can be adjusted to a proper degree by the diluent (c), for example, by dip coating. Coating, flow coating, roll coating, bar coating, screen printing, curtain coating, etc. The circuit board of the circuit is fully formed by volatilizing (relatively drying) the organic solvent contained in the composition at a temperature of 60 to 1 Torr to form a coating film having a tack-free. Further, a coating film can be formed by applying the above-mentioned composition to a carrier film and drying it to form a rollable film, which is deposited on a substrate. Thereafter, the contact lens (or non-contact type) is selectively exposed to the active energy ray through the photomask formed with the pattern 2, and the exposed portion is diluted 23 201015216 ^=如〇.3~3% An aqueous solution of soda carbonate was developed to form a resist pattern. Hardening; 3, i is a hardened coating film which is heated by a temperature of, for example, about 140 to a temperature to make it heat-resistant, resistant, resistant to smoking, (four), and electrical characteristics. The substrate of the above-mentioned circuit is used to use paper age, paper epoxy resin, dioxin glass fiber, glass polytheneamine, epoxy glass cloth/non-woven fabric, glass cloth oxygen synthetic fiber A copper-clad laminate for cyan-equivalent frequency turbulence, and examples thereof include a polyimide film, a pετ film, a glass substrate, a ceramic substrate, and a wafer plate. ,

Further, as the irradiation light source used for the active energy ray, a low-pressure mercury, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp or the like is suitable. In addition to this, it is also possible to use a laser beam or the like as an active energy ray. As the developing method, it can be carried out by dipping, shower, spray, brush, or the like; as the developing solution, for example, potassium hydroxide, sodium hydroxide, or the like can be used. A diluted alkaline aqueous solution such as sodium carbonate, carbonic acid unsalted, sodium phosphate, sodium sulphate, ammonia, or amine. (Cured product) The cured product of the black solder resist composition thus obtained is an epoxy compound containing 8% by weight of a coloring agent, and contains two or more kinds of coloring agents. Specifically, the coloring agent contained is the following mixing ratio. Yellow colorant 1 weight portion and purple colorant 〇.〇1~1〇 weight portion; yellow colorant 1 weight portion and blue colorant 〇.〇1~1〇 weight portion and red colorant 0.01~10 weight portion; 1 part by weight of green colorant and 0.01 to 10 parts by weight of purple colorant; 1 part by weight of yellow coloring agent and purple coloring agent 〇. 〇1~1 〇 weight part and blue coloring agent 0.01~10 weight part; or green coloring agent 1 weight portion and red colorant 0.01 to 10 parts by weight and blue colorant 0.01 to 10 parts by weight, 24 201015216 The cured product is as described above, L* value is 33 or less, and a* value and b* value are all bauxite Within the scope of 3. [Examples] The present invention is specifically described in the following examples and comparative examples, and the present invention is not limited by the following examples. In addition, the term "part" used hereinafter is not particularly limited, and all of them mean "weight portion". <Synthesis of Resin-Containing Resin> The carboxyl group-containing resin (Α) of the present invention is produced in accordance with the following synthesis examples. 210 parts of Cresol Novolac type epoxy resin (manufactured by Otsuka Oil ❹Ink Chemical Industry Co., Ltd., ΈΡΚΧΟΝ" (registered trademark) N-680 'epoxy equivalent: 210) In a four-necked flask equipped with a stirrer and a reflow cooler, 96.4 parts of ethylene glycolate was added to heat and dissolve. Then, 0.46 parts of hydroquinone as a polymerization inhibitor was added. And 1.38 parts of triphenylphosphine as a reaction catalyst. The mixture was added to 95-105 ° C, and 72 parts of acrylic acid was slowly dropped to react for about 16 hours until the acid value became 3.0 mg KOH / g. The reaction product was cooled to 80 to 90 ° C, and 76 anhydrous tetrahydrophthalic anhydride (Sf) was added to react for 8 hrs. After cooling, the reaction solution was taken out (referred to as "coating". Paint A" (vanish A)). The acid value of the solid matter in the photosensitive resin thus obtained was 78 mg KOH/g, and the non-volatile portion was 65%. &lt;Examples 1 to 7 and Comparative Examples 1 to 5&gt; The paint A obtained by the synthesis of the carboxyl group-containing resin and the components shown in Tables 1 and 4 were mixed according to Table 2 and Table 3. The ratio was mixed with 3 roller mills to obtain a black solder resist composition. A [Table 1] Raw material name / abbreviated component classification Raw material manufacturer R-2000 A1 Main resin (A) DIC #907 B1 (B) Ciba 25 201015216 ITX B2 Photopolymerization initiator Lambson Fine Chemicals EAB-W B3 Industry #784 B4 Ciba Diethylene Glycol Ether Acetate Cl Solvent (C) AP Chemicals #150 C2 Idemitic Petrochemical TADH-4 C3 Reactive Diluent Monomer (C) East Asia Synthetic TCBN-75 D1 Epoxy Resin (D Oiled SHELL EPOXY TEPIC-HPT D2 曰Chemical 蒽鲲Yellow AGR El Yellow Pigment (E) Ciba Fastogen Green S E2 Green Pigment DIC CROMOPHTAL VIOLET B E3 Purple Pigment Ciba Irgalite Red 2BP E4 Red Pigment Ciba Fastogen Blue 5380 E5 Blue Pigment DIC #1255 FI Black Pigment (F) Columbian Chemicals

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A1 154.0 154.0 154.0 154.0 154.0 154.0 154.0 B1 15.4 15.4 15.4 15.4 15.4 15.4 15.4 B2 0.9 0.9 0.9 0.9 0.9 0.9 0.9 B3 B4 0.2 0.2 0.2 0.2 0.2 0.2 Cl 9.5 9.5 9.5 9.5 9.5 9.5 9.5 C2 10.0 10.0 10.0 10.0 10.0 10.0 10.0 C3 20.0 20.0 20.0 20.0 20.0 20.0 20.0 D1 26.6 26.6 26.6 26.6 26.6 26.6 26.6 D2 15.0 15.0 15.0 15.0 15.0 15.0 15.0 El 3.0 3.0 1.2 2 E2 1.8 3.5 3.5 26 201015216 E3 1.0 0.6 4.5 6 E4 0.8 2.5 1.4 E5 1.0 1.5 0.5 1.0 F1 0.4

[Table 3] Comparative Example 1 (Previous product) Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 A1 154.0 154.0 154.0 154.0 154.0 B1 15.4 15.4 15.4 15.4 15.4 B2 0.9 0.9 0.9 0.9 0.9 B3 0.09 0.09 0.09 B4 0.20 0.20 Cl 9.5 9.5 9.5 9.5 9.5 C2 10.0 10.0 10.0 10.0 10.0 C3 20.0 20.0 20.0 20.0 20.0 D1 26.6 26.6 26.6 26.6 26.6 D2 15.0 15.0 15.0 15.0 15.0 El E2 E3 2.0 10.0 E4 E5 FI 1.2 1.2 0.8 [Table 4] Product Name Pigment Classification CI Pigment No. 蒽醗黄 AGR Yellow pigment brewing (anthraquinone) Yellow 147 27 201015216

Fastogen Green S Green Pigment (E) phthalocyanine green Green 7 CROMOPHTAL VIOLET B Purple Pigment Dioxazine Violet 37 Irgalite Red 2BP Red Pigment Monoazo Lake Red 48:2 Fastogen Blue 5380 blue pigment phthalocyanine blue Blue 15:3 #1255 black pigment (F) carbon black Examples 1 to 7 and comparative examples 1 to 5 of the solder resist composition are in accordance with the following evaluation criteria Evaluate its performance. The results are shown in Tables 5 and 6. Evaluation of performance: (1) Color difference meter The above-mentioned fine solder resist compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were respectively applied to the entire copper substrate by screen printing, and were subjected to hot air circulation. It was dried in a drying oven at 80 C for 30 minutes. Then, it was exposed by exposure to an ultraviolet light having a wavelength of 365 nm on a solder resist at a light amount of 500 mJ/cm 2 using an integrated photometer manufactured by 〇rc. Thereafter, the solution was developed in an amount of 1 wt% of a 0.2 MPa Na2CO3 aqueous solution over 60 seconds, and then applied to a hot air circulating drying oven for 150 minutes. Heat hardened to obtain a hard coating film. For the hardened coating film obtained by this method, the L*a*b* color system on the copper in the following color difference meter is measured in accordance with JIS Z8729, and the L* value indicating the brightness is used as an indicator of the blackness. Evaluation. The smaller the L* value is, the better the blackness is. Color color difference meter: 45° ring illumination vertical light receiving type high performance color color difference meter (Konica Minolta CR-221) (2) Resolving property The solder resist compositions of the above Examples 1 to 7 and Comparative Examples 1 to 5 Printed on the 28 201015216 screen printing plate _ side circuit substrate 'in the hot 嶋 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Red is exposed with 5GGml/em2 light amount of the exposed wire. Thereafter, it was developed in an aqueous solution of Na2C〇3 at a pressure of 1% by weight and a pressure of 2 MPa. Visually determine the line and space remaining in the exposure section (3) Absorbance ”

The solder resist compositions of the above Examples 1 to 7 and the ratios 1 to 5 were respectively coated with an applicator and then dried in a hot air circulating drying oven at 8 Torr: 30 minutes to dry. Coating film. The absorbance reference line at 500 to 300 nm was measured on the same glass plate as the above glass plate using the following ultraviolet visible spectrophotometer and integrating sphere device. The absorbance of the glass plate with the prepared dried coating film was measured, and the absorbance of the dried coating film was calculated from the reference line to obtain an absorbance at a target wavelength of 410 nm. In order to prevent the difference in absorbance due to the difference in the thickness of the coating film, this operation is a four-stage coating film thickness of the applicator, and a graph of the coating film thickness and the absorbance at 410 nm is prepared, and the film thickness is calculated from the approximation to 25 vm. The absorbance of the dried coating film is taken as its respective absorbance. Ultraviolet-visible spectrophotometer: Ubest-V-570DS integrating sphere device: ISN-470 manufactured by JASCO Corporation. (4) Heat resistance The solder resists of the above Examples 1 to 7 and Comparative Examples 1 to 5 The composition of the agent was applied to the entire printed circuit board on which the circuit was formed by screen printing, and dried in a hot air circulating drying oven for 30 minutes. On these substrates, the film was exposed to light on the solder resist at a light amount of 500 mJ/cm2 through a film having a solder resist pattern. Subsequently, a 1% by weight spray of 22 MPa of Na2CO3 aqueous solution was developed for 1 minute to form a solder resist pattern. This substrate was thermally cured at 150 ° C for 60 minutes to prepare a substrate for evaluation. The obtained evaluation substrate was coated with a rosin flux and immersed in a soldering pot previously heated to 260 ° C for 30 seconds to obtain a propylene glycol monomethyl propylene glycol. Ether) After the flux is washed, the peeling and discoloration of the resist layer are evaluated by visual inspection 29 201015216. (5) Gold plating resistance The above-mentioned fine-grained 1 to 7 and the ratio (4) of the brown plate, the wire cloth was formed on the printed circuit board on which the circuit was formed, and the air-dried type was dry-dried and dried for 30 minutes. On these substrates, the film was exposed through a negative film of 5 μm/cm 2 on the anti-blocking agent. Then, the pseudo-weight % of the spray pressure G is in a fine image of 1 minute, and the welding is __. This substrate was thermally hardened at i5 ° C for 6 G minutes and was continued as a cake side. The obtained evaluation substrate was subjected to electroplating by a commercially available electroless nickel plating solution and an electroless gold plating solution, and the peeling and discoloration of the resist layer were visually evaluated.曰 [Table 5] Characteristic target test method Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Resolution 60 seconds development 50 μιη Company internal test 500 mJ/cm2, 60 sec Minimum residual county 50 60 40 60 70 700mJ/cm2, 60 sec (μ®) 40 40 30 40 50 Resolving 100-second imaging 60μπι 500mJ/cm2s 60 sec or less 80 90 80 90 90 700mJ/cm2, 60 sec 60 60 60 60 70 Color Meter (μιη) Color Difference Meter 19.7 20.2 20.7 21.6 20.8 White e Black L* 33 or less 31.02 31.32 31.19 30.32 30.26 Red Green a* 0±3 -0.82 -1.33 -0.79 -2.10 -1.96 Yellow e Blue b* 0±3 1 '69 -1.22 -0.79 2.10 -1.96 Heat resistance without peeling company internal test no peeling no peeling no peeling no peeling no peeling no peeling gold plating resistance no peeling company internal test no peeling no peeling no peeling no peeling no peeling no peeling Halogen amount ( Ppm) 900ppm Calculated value 337 380 342 2448 4763 Color difference meter: SCI mode (including specular reflection) made by CM-2600dKONICAMINOLTA 30 201015216

[Table 6] Characteristic target test method Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Resolution 60 seconds development 50 μιη The following company internal test minimum residual county (μιη) 500 mJ/cm 2 , 60 Sec 100 100 50 30 100 700mJ/cm2, 60 sec 90 90 40 30 80 Resolving 100 second imaging 60μπι below 500mJ/cm2, 60 sec 100 100 80 40 100 700mJ/cm2, 60 sec 100 100 60 30 100 Color meter (μπ 〇 color difference meter 20.1 19.0 20.0 21.3 20.6 white e black L* 33 or less 29.98 29.91 34.28 30.88 28.16 red θ green a* 0+3 -0.80 -1.39 -1.55 12.69 3.38 yellow g blue b* 0±3 -0.91 - 0.17 1.12 -13.35 -2.32 Heat resistance without peeling Company internal test Some peeling Some peeling No peeling No peeling No peeling Some peeling Gold plating resistance No peeling company Internal test Some peeling No peeling No peeling No peeling No peeling No peeling Halogen Amount (ppm) 900ppm The following calculated value is 355 444 444 348 342 color color difference meter: CM-2600d KONICA MINOLTA system SCI mode (including specular reflection light) It is clear from Table 5 that the black solder resist composition of the present invention It has sufficient blackness and excellent resolution, and has excellent properties such as excellent heat resistance and gold plating resistance. For this reason, as can be seen from Table 6, the comparison of black coloring with black coloring is sufficient. The degree of blackness is not the same as that of the examples. The heat resistance and gold plating of the black colorant are inferior to the examples, and the heat resistance and minerality are also poor. Comparative Example 3 having a smaller blending amount has sufficient resolution, and has a lower chroma than the examples. In Comparative Examples 4 and 5, no black colorant is mixed, and 31 201015216 is colored in a purple color. In the case where a small amount of coloring agent is mixed as in Comparative Example 4, 'there is no blackening, and it cannot function as a black &amp; solder resist. As in Comparative Example 5, a large amount of purple coloring agent is mixed. Although it is close to black: its resolution is worse than that of the embodiment. ' [Simple description of the figure] The first picture shows the Munsell color system. [Main component symbol description]

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Claims (1)

201015216 VII. Patent application scope: 1. A black solder resist composition characterized by: a resin containing a carboxyl group (A); ' 'photopolymerization initiator (B); a diluent (C); ... 1 a polyfunctional epoxy compound (D) having a plurality of epoxy groups in the molecule; and a coloring agent CE), wherein the coloring of the enamel is selected from the group consisting of yellow (10) coloring agent ί j coloring agent and blue coloring agent and red coloring Agent, green•=toner' and any group of green colorant and red colorant: 2·- a black solder resist composition characterized by having a carboxyl group-containing resin (A); ' ' a photopolymerization initiator (B); a diluent (C); a compound ()); wherein the toner (Ε) is obtained by containing a yellow-yellow color selected from the weight of the ❹I. a blue coloring agent and a purple coloring agent in a 1G weight portion, and a black solder resist composition according to item 1, which is a group of a purple coloring agent and a yellow coloring agent. Meaning 4. The composition of the household in the surrounding area, in which the purple part of the measuring part _ ===== 33 201015216. 5. The black solder resist composition according to claim 1, wherein the combination of the green colorant and the red colorant is combined with the blue colorant in the combination of the coloring agent. 6. The black solder resist composition according to claim 2, wherein the combination of the colorant (Ε) is a weight portion of the green colorant and the weight of the 〇〇1 to 1 () The combination of red colorants is combined with a blue colorant of 0. 01 to 10 parts by weight.黑色 7. The black solder resist composition according to any one of claims 1 to 6, wherein the hardened matter has an L* value of 33 or less, and the a* value and the b* value are both 〇. Within the range of ±3. 8. The black solder resist composition according to any one of the preceding claims, wherein a black colorant is additionally added. 9. A cured product of a black solder resist composition, characterized in that: the agent comprises a yellow colored tinted coloring agent, a yellow coloring agent and a coloring agent, a green coloring agent and a purple color. A colorant, and any one of the group of colorants and red colorants. 10 doses 1=: hardened material of solder resist composition: the hardened material contains colored ϊ ΐ ΐ ΐ ΐ 有 有 有 ΐ ΐ ΐ ΐ 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有1G weight part of the blue color agent and 0.01 to 10 parts by weight | coloring agent and 0.01 to 10 weights · B 1 resetting green agent and discussion ~ 1 〇 weight part 2 color f I1 weight part of the green coloring purple fine The coloring agent and 34 201015216 coloring agent and 0.1 to 10 parts by weight of the purple coloring agent are added to the 01 to 10 parts by weight of the blue coloring agent. 13. The hardener of the black solder resist composition according to claim 9 of the invention, wherein the coloring agent contained in the hardened material is obtained by adding a blue colorant to the green colorant and the red colorant. Form 》 14. The cured product of the black solder resist composition as described in claim 1 wherein the coloring agent contained in the hardened material is based on 1 part by weight of the green colorant and 0.1 A red coloring agent of 10 to 10 parts by weight is added to a white coloring agent of 0.01 to 10 parts by weight. The cured product of the black solder resist composition according to any one of claims 9 to 14, wherein the L* value is 33 or less, and the a* value and the b* value are both 0. Within the range of ±3. A cured product of the black solder resist composition according to any one of claims 9 to 15, which contains a black colorant. 17. The black solder resist according to any one of claims 9 to 16, wherein the hardened material of the resist composition contains 0. 1 to 8 wt% of a coloring agent. 35