TW201007356A - Photocurable resin composition, dry film and cured object thereof, and printed circuit board with the same - Google Patents

Abstract

The present invention provides a photocurable resin composition which has excellent finger-touching drying property of dried coating film and does not have the problems of photomask adhesion, etc. in exposure when the contact exposure is executed. The invention also provides a dry film and a cured object of the photocurable resin composition, and a printed circuit board which is obtained from the curved coating with the solder resist formed by the dry film and the cured object. The photocurable resin composition comprises a cellulose derivative (A). Preferably, the cellulose derivative (A) is solvent-soluble, and the glass transition temperature Tg is preferably above 100 DEG C. Furthermore, the photocurable resin composition is preferably alkali-developable. The photocurable resin composition is obtained through coating the photocurable resin composition on the carrier film and drying. Additionally, the invention also provides the printed circuit board of the curved coating obtained through thermal curing after the photocurable resin composition or the dry film is photocured.

Description

201007356 VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable resin composition which can be developed by a dilute aqueous alkali solution, particularly a photo-curing agent which is photocured by ultraviolet exposure or laser exposure. The composition, its dry film and cured product, and the use of their printed circuit boards. 0 [Prior Art] With the recent rapid advancement of semiconductor components, electronic devices are becoming smaller, lighter, higher-performance, and more versatile. Along with this tendency, the printed circuit board is also highly densified, and the surface of the component is mounted. In the manufacture of high-density printed circuit boards, solder resists are generally used, and dry film type solder resists or liquid photoresists have been developed. Among these, in view of environmental problems, an alkali-developing photosensitive composition using a dilute aqueous alkali solution as a developing solution is mainly used, and several components have been proposed in the past (see Patent Documents 1 to 3). The photosensitive composition is currently used in a large amount as a solder resist in a practical printed circuit board. The method of forming the solder resist using the soldering layer is applied to the substrate on which the circuit is formed and dried, and then the contact exposure of the image sorting tool to vacuum adhesion and exposure is mainstream. At this time, when the dryness of the dry coating film is poor, the image sorting tool is in close contact with the coating film, which has the disadvantage that the image sorting tool cannot be peeled off, or the dry coating film is peeled off from the substrate. In order to improve the dryness of the dry coating film 201007356, a method of adding a resin other than a photocurable resin such as a phenoxy resin to a photosensitive composition is known (for example, refer to Patent Document 4). However, when the resin is added to the photosensitive composition, the dryness of the dry coating film can be improved, but the developability is poor, and the time until drying and development (drying management width) after drying is shortened. problem. Further, when the dry film type solder resist having a dry coating film formed on the carrier film is overlapped and exposed by the image sorting tool exceeding the carrier film, there is no disadvantage of being intimately attached to the image sorting tool as described above. However, when the dry film type solder resist is vacuum-heated and laminated on a circuit board having irregularities on which a circuit is formed, the dryness of the touch is poor, and the substrate is bonded to the substrate in a state where the vacuum decompression is insufficient. There is a disadvantage that air bubbles remain between the circuits. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is excellent in dryness to the touch, and it does not have a photocurable resin composition which is caused by problems such as the spreadability of the image classification tool during exposure, even when exposed to -6-201007356. An object of the present invention is to provide a dry film and a cured product which are excellent in various characteristics described above by using the photocurable resin composition, and a cured film formed of a solder resist or the like by the dry film or cured product. A printed circuit board. In order to achieve the above object, the present invention provides a photocurable resin composition characterized by containing a cellulose derivative (A). In a preferred embodiment, the cellulose derivative (A) is solvent-soluble, and the glass transition temperature Tg of the cellulose derivative (A) is preferably 1 〇〇 ° C or more. Further, the photocurable resin composition preferably has alkali developability. The photocurable resin composition may be in the form of a liquid or in the form of a dry film. In the photocurable dry film, the photocurable resin composition is applied onto a carrier film and dried. Further, the present invention provides a cured product obtained by photohardening the above-mentioned photocurable resin composition or dry film. Furthermore, the present invention provides a printed circuit board comprising a cured film obtained by photohardening a photocurable resin composition or a dry film. Moreover, there is provided a printed circuit board characterized by having a hardened film containing a cellulose derivative (A). Further, in the present invention, the printed circuit board refers to a substrate on which a conductor pattern is formed on a surface of an electrically insulating substrate by using a printing technique such as a screen printing method or a photolithography method, and is rich in a flexible circuit board and Flexible circuit board. 201007356 [Effect of the Invention] The photocurable resin composition of the present invention contains a cellulose derivative, and the coating film after drying has excellent dryness to the touch, and even if contact exposure is performed, the image classification tool is not exposed during exposure. The problem is that, unlike the case of adding a phenoxy resin, the developability is excellent, and the time until drying and development (drying management width) after drying is increased. Therefore, the photocurable resin composition of the present invention can be usefully used for forming a hardened film such as a solder resist of a printed circuit board. [Best Mode for Carrying Out the Invention] As described above, the photocurable resin composition of the present invention is characterized in that a dry coating film excellent in finger-drying property can be obtained, and the image classification tool can be posted for contact exposure. In the case of a problem such as sex, a cellulose derivative is contained, and other photocuring components and the like may contain various conventional components. The components of the photocurable resin composition of the present invention are described below. (A) Cellulose derivative The cellulose derivative (A) used in the present invention is soluble in an organic solvent and preferably has a high glass transition temperature (Tg). The cellulose derivative is, for example, the following cellulose ether, carboxymethyl cellulose, cellulose ester or the like. Cellulose ethers such as ethyl cellulose, hydroxyalkyl cellulose, etc., and commercial products of ethyl cellulose such as Ethocel (registered trademark) 4, Ethocel 7, Ethocel 10, Ethocel 14, Ethocel 20, Ethocel 45,

Ethocel 70, Ethocel 100, Ethocel 200, Ethocel 300 (both 201007356 are trade names of Dow Themical) 'Commercials based on base-based cellulose such as Methollose SM, Methollose 60SH, Methollose 65SH, Methollose 90SH, Methollose SEB, Methollose SNB (all are the trade names of Shin-Etsu Chemical Co., Ltd.) and so on. Further, a commercial product of carboxymethyl cellulose such as CMCAB-641-0.2 (trade name manufactured by Eastman Co., Ltd.), Sunrose F, Sunrose A, Sunrose P, Sunrose S, and Sunrose B (all manufactured by Nippon Paper Chemical Co., Ltd.) Product name) and so on. Further, a preferred cellulose derivative is a cellulose ester obtained by esterifying a hydroxyl group of cellulose with an organic acid, and specifically, for example, a compound represented by the following formula (1).

【化1】

(In the formula, R is a hydrogen or an organic acid ester group, and is composed of at least two or more selected from the group consisting of hydrogen and organic acid vinegar. The η is an integer of 1 or more, and the upper limit is defined by the molecular weight described below). In the cellulose ester represented by the above formula (1), the base content of the cellulose resin is 0 to 6 wt%. The organic acid ester preferably has an ethyl hydrazide content of from -9 to 201007356 of 0 to 40% by weight, and a propylene group or/and a butyl group content of from 〇 to 555% by weight. The "wt%" referred to herein is the weight % of hydrogen or organic acid ester based on the weight of the cellulose. Commercial products of the cellulose ester, such as CA-3 98-3, CA-3 98 -6 'CA-398-10, CA-3 98-300, CA-3 94-60S, etc. of cellulose acetate. 'CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1, CAB-500-5, CAB-381-0.1, CAB-381-0.5, CAB of cellulose acetate butyrate -381-2, CAB-381-20, CAB-381-20BP, CAB-321-0.1, CAB-171-15, etc., CAP-504-0.2, CAP-482-0.5, CAP- of cellulose acetate propionate 482-20 (all of the above cellulose derivatives are trade names of Eastman Co., Ltd.) and the like. Among these, cellulose acetate butyrate and cellulose acetate propionate are preferred for solubility of the solvent, and cellulose acetate propionate is more preferable for odor. The number average molecular weight of the cellulose derivative is not particularly limited, and is preferably from 5,000 to 500,000, more preferably one 〇, 〇〇〇~1 〇〇, 〇〇〇. When the molecular weight is less than the above range, it is difficult to obtain the desired dryness of the touch (no wrinkle), and when it is more than the above range, the solubility and compatibility of the solvent are likely to be deteriorated, which is not desirable. Further, the glass transition temperature Tg of the cellulose derivative is preferably 70 ° C or more and less than 200 ° C, more preferably 10 ° C or more and less than 180 ° C. When the glass transition temperature is less than 70 °C, it is difficult to obtain sufficient wrinkle-free properties, and when it is 200 ° C or more, the wrinkle resistance of the cured coating film may be caused. In addition, the glass transition temperature Tg referred to in the present invention refers to a glass transition temperature measured by a thermomechanical analysis (DSC) based on the method described in "5.17.5 201007356 DSC method" of JIS C648 1 : 996. . The cellulose derivative used in the present invention is derived from a natural product, but is preferred in terms of a depleted surface of a fossil fuel. Further, the starting material used in the cellulose derivative of the present invention can be produced from a recycled product such as a regenerated slurry, and a preferred composition can be provided in the environment in which the co2 is reduced. Further, even if the cellulose derivative used in the present invention has a high softening point, the resulting photocurable resin composition does not have a problem of developability as an alkali developable solder resist, and an effect which is not unexpectedly obtained can be obtained. Further, the sensitivity is not lowered, and since the solvent is soluble, the image is not glare, and there is no problem of electrical characteristics or solder heat resistance. The above-mentioned cellulose derivative (A) may be used singly or in combination of two or more kinds. The amount of the cellulose-derived compound (A) is from 1 to 50 parts by mass, preferably from 2 to 40 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). When the amount of the cellulose derivative (A) is less than 1 part by mass, it is difficult to form a flexible cured film excellent in wrinkle-free properties, and when it is more than 50 parts by mass, the mechanical properties of the cured product are liable to lower. Not for the sake of the enterprise. The photocurable resin composition of the present invention is not limited to a specific constituent component, and is not limited to a specific constituent component, and is basically a photocurable component or a thermosetting component. In the case of a flux, the cellulose derivative (A), the carboxyl group-containing resin (B), the photopolymerization initiator (C), and the compound (D) having two or more ethylenically unsaturated groups in the molecule are generally contained. A thermosetting component (E) such as an epoxy compound, a thermosetting catalyst, a chelating agent, an organic solvent, etc., depending on the -11 - 201007356 ' can be prepared by combining the types and amounts of the components A cured product of the above characteristics is obtained. The hardened material having the above characteristics by combining the components and the blending amount, etc., can be easily confirmed by an appropriate test by referring to the following examples and comparative examples, and thus the detailed description is omitted. The main constituent components of the photocurable resin composition of the present invention will be briefly described below. (B) Carboxyl group-containing resin The photocurable resin composition containing a cellulose derivative of the present invention can be a conventional resin compound having a carboxyl group in a molecule. The carboxyl group-containing resin may be any one of a resin containing no ethylenic unsaturated double bond, a carboxyl group-containing resin (B-1), or a photosensitive carboxyl group-containing resin (B-2) having an ethylenically unsaturated double bond. There is no particular limitation, and in terms of photocurability or developability, a photosensitive carboxyl group-containing resin (B-2) having an ethylenically unsaturated double bond in a molecule is more preferable. Therefore, the unsaturated double bond is preferably one derived from acrylic acid or methacrylic acid or such derivatives. In addition, when a resin (B-1) containing no ethylenic unsaturated double bond and containing only a carboxyl group is used, in order to form a photocurable composition, it is necessary to use two or more of the following in the molecule. Saturated group of compound (D). Specific examples of the carboxyl group-containing resin (B) include the compounds listed below (either an oligomer and a polymer). (1) By using an unsaturated carboxylic acid such as (meth)acrylic acid or a compound having an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene The resulting carboxyl group-containing -12-201007356 resin was copolymerized. (2) By including a diester such as an aliphatic diisocyanate, a branched aliphatic diester, an alicyclic diisocyanate or an aromatic diisocyanate, and a dimethylolpropionic acid or a dimethylolbutyric acid a carboxyl group-containing compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyene-based polyol, an acrylic polyol, a bisphenol A-based oxyalkylene glycol, and a phenolic hydroxyl group and an alcohol A carboxyl group-containing urethane (3) obtained by a polymerization addition reaction of a compound such as a hydroxyl group compound, and a bisphenol A, an bisphenol A type epoxy resin bisphenol A type epoxy resin, and bromination (meth)propene of a bifunctional epoxy resin such as a bisphenol A epoxy resin, a double j epoxy resin, a bisphenol S epoxy resin, or a bixylenol epoxy bisphenol epoxy resin or A photosensitive carboxyl group-containing urethane obtained by a polymerization addition reaction of a partial acid anhydride modified product, a carboxyl group-containing diol compound, and a two product. (4) In the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and a (meth)acryloyl group in the molecule, such as an alkyl (meth) acrylate, is added to the terminal. (Methylated) carboxyl group-containing urethane resin. (5) In the synthesis of the resin of the above (2) or (3), a compound having one isocyanate group and one or more (meth) propyl groups in a molar reaction molecule such as galketone isocyanate and pentaerythritol triacrylate, A terminal (meth)acrylated carboxyl group-containing amine ethyl ester resin. Isocyanic acid isocyanate diolized alcohol, polyaddition alcoholic alcohol resin. Hydrogenated F-type resin, ethylenic acid ester ethyl ester tree, one hydroxyl group, acrylic acid, isophor, etc. in the olefinic carboxylic acid-13-201007356 (6) The following two or more functional groups A photosensitive (solid) epoxy resin is reacted with (meth)acrylic acid to form a photosensitive carboxyl group-containing resin obtained by adding a dibasic acid anhydride to the produced hydroxyl group. (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, reacting with (meth)acrylic acid, and adding a dibasic acid anhydride to the produced hydroxyl group Photosensitive carboxyl-containing resin. (8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin described below with a dicarboxylic acid to form a dibasic acid anhydride in the produced first-order hydroxyl group. (9) A photosensitive carboxyl group-containing resin formed of a compound having one epoxy group and one or more (meth)acrylic groups in the component is further added to the above resins (1) to (8). Further, in the present specification, the (meth) acrylate is a general term for acrylate, methacrylate, and the like, and the other similar performances are also the same. Since the carboxyl group-containing resin (B) has a plurality of free carboxyl groups in the side chain of the rear bond/polymer, it can be developed by a dilute aqueous alkali solution. Further, the acid salt of the carboxyl group-containing resin (B) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 4 5 to 1 20 mg ΚΟH/g. When the acid group of the carboxyl group-containing resin (B) is less than 40 mgKOH/g, alkali development cannot be performed, and when it is more than 200 mgKOH/g, when the exposure portion is dissolved by the developer, the line is made thinner than necessary. Further, depending on the case -14,075,563, it is impossible to distinguish between the exposed portion and the unexposed portion, and finally, dissolution and peeling occurs in the developer, and a normal photoresist pattern cannot be formed, which is not desirable. Further, the weight average molecular weight of the above carboxyl group-containing resin (B) varies depending on the resin structure, and is generally preferably in the range of 2,000 to 150,000, more preferably in the range of 5,000 to 10,000,000. When the weight average molecular weight is less than 2,000, there is a case where the coating film has no shrinkage property (dryness of the touch), and the moisture resistance of the coating film after the exposure is not good, and the film edge is reduced during development, and the resolution is high. Very bad. Further, when the weight average molecular weight is more than 150,000, the developability is remarkably deteriorated, and the storage stability is not good. The compounding amount of the carboxyl group-containing resin (B) is preferably in the range of 20 to 60% by mass of the total composition, more preferably in the range of 30 to 50% by mass. When it is less than the above range, the coating film strength is lowered, which is not desirable. Further, when the amount is larger than the above range, the viscosity of the composition is high, and the coatability and the like are lowered, so that it is not desired. Further, the above-mentioned carboxyl group-containing resin (B) is not limited to those mentioned above. Further, it may be used alone or in combination of two or more. (C) Photopolymerization Initiator The photopolymerization initiator (C) is one selected from the group consisting of an oxime ester photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, and a fluorenyl phosphine oxide-based light. A photopolymerization initiator in which a polymerization initiator is grouped is preferred. The oxime ester photopolymerization initiator is, for example, an oxime ester photopolymerization initiator having a group represented by the following general formula (2), for example, as a commercial product -15-201007356

CGI-3 25, Irgacure OXEOl, Irgacure OXE02, etc. manufactured by Ciba. Specialty Chemicals, or N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators may be used singly or in combination of two or more kinds. [Chemical 2] A C = N - Ο C - R2 .. (2)

I R =o Chinese

a number of carbons may be substituted with an alkyl group having a carbon number of from 1 to 20, which may be substituted with one or more hydroxyl groups, or may be substituted in the form of an anthracene benzene, a sub-hydrogen display, a phenyl group or a halogen atom. Having at least one oxygen atom in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a benzhydryl group (also an alkane having 1 to 6 carbon atoms) Or a phenyl group), R2 represents a phenyl group, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 2 carbon atoms (one or more hydroxyl groups may be used) Substituting, may also have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having a carbon number of from 5 to 8, an alkanol group having a carbon number of 2 to 20 or a benzhydryl group (may also be carbon a 1 to 6 alkyl group or a phenyl group)) - i-aminoacetophenone photopolymerization initiator, such as 2-methyl-1-[4-(methylthio)phenyl]-2-? Polinylacetone-1,2-benzyl-2-oxomethyl-1-(4-cylinylphenyl)-butyl-1-pyrene, 2-(-methylamino)-2 -[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, hydrazine, hydrazine dimethylamino acetophenone, etc.As a commercial product, Irgacure 907, -16- 201007356 by Ciba· Specialty·Chemicals

Irgacure 3 69, Irgacure 3 7 9 and so on. Thiol-based phosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide , bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. As a commercial product, Lucirin TPO manufactured by BASF Corporation, Irgacure-819 manufactured by Ciba* Specialty* Chemicals, and the like. The amount of the photopolymerization initiator (C) is preferably in the range of 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the above-mentioned φ carboxyl group-containing resin (B). . When the amount is less than 0.01 parts by mass, the photocurability on the copper is insufficient, the coating film is peeled off, and the coating film properties such as chemical resistance are lowered, so that it is not desired. In addition, when it is more than 30 parts by mass, the light absorption on the surface of the coating film of the photopolymerization initiator (C) tends to be intense, and the deep hardenability tends to be lowered, so that it is not desired. In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (2), the amount thereof is 0.01 to 20 parts by mass per 100 parts by mass of the carboxyl group-containing resin φ (B). The range is preferably, and more preferably in the range of 0·01 to 5 parts by mass. Further, in the photocurable resin composition of the present invention, a photopolymerization initiator other than the above compound, or a photoinitiation aid and a sensitizer can be used. For example, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, an acetal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like. Specific examples of benzoin compounds such as benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether. -17- 201007356 Specific examples of acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone 1,1-dichloroacetophenone. Specific examples of the hydrazine compound are 2-methyl hydrazine, 2-ethyl hydrazine, 2- 3-butyl hydrazine, and 1-chloroindole. Specific examples of thioxanthone compounds, such as 2,4-dimethylpyrone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone . Specific examples of the acetal compound are acetophenone dimethyl acetal and benzyl dimethyl acetal. Specific examples of the benzophenone compound, such as benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylformamide Specific examples of the base-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide 3-grade amine compound, such as an ethanolamine compound, having a dialkylaminobenzene a compound such as 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) Dialkylaminobenzophenone, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)- a dialkylamine group-containing coumarin compound such as 4-methylcoumarin), ethyl 4-dimethylaminobenzoate (kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino group Ethyl benzoate (Qantacure D Μ B made by internari ο na 1 bi 〇synthetics), n-butyloxyethyl 4-dimethylaminobenzoate (Quantacure BEA, manufactured by Internarional Biosynthetics), p- Dimethylaminobenzene -18 - 201007356 Isoamyl acetoacetate (kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-methylaminobenzoic acid 2-ethylhexanoic acid (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethyl Aminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.). Among the other photopolymerization initiators mentioned above, a thioxanthone compound and a tertiary amine compound are preferred. The thioxanthone compound is contained in the photocurable resin composition, and is preferably in terms of deep hardenability, wherein 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chloro A thioxanthone compound such as thioxanthone or 2,4-diisopropylthioxanthone is preferred. The blending ratio of the thioxanthone compound is preferably 20 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the carboxyl group-containing resin (B). When the blending ratio of the thioxanthone compound is too large, the thick film hardenability is lowered and the cost of the product is also increased, so that it is not desired. The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure in which a dialkylaminobenzophenone compound and a dialkylamine group having a maximum absorption wavelength of 305 to 41 Onm are contained. The coumarin compound is better. The dialkylaminobenzophenone compound is preferred because it has low toxicity to 4,4'-diethylaminobenzophenone. A dialkylamine-containing coumarin compound having a maximum absorption wavelength of from 3 to 50 nm, which has a maximum absorption wavelength in the ultraviolet range, can provide a photocurable resin composition which is less colored, is colorless and transparent, and is used. A colored solder mask that reflects the color of the coloring pigment itself. In particular, 7-(diethylamino)-4·methyl-2H-1-benzopyran-2-one has an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm. -19- 201007356 The mixing ratio of the tertiary amine compound is preferably 0.1 to 2 parts by mass, more preferably 0.1 to 10 parts by mass, based on the carboxylic acid-containing resin (B). When the mixing ratio of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect cannot be obtained. On the other hand, when it is more than 20 parts by mass, the light absorption on the surface of the dried coating film is severe due to the tertiary amine compound, and the deep hardenability tends to be lowered. These photopolymerization initiators, photoinitiation aids, and sensitizers may be used singly or in combination of two or more kinds. In the photocurable resin composition of the present invention, in order to improve the sensitivity, conventional N-phenylglycine, phenoxyacetic acid, sulfurized phenoxyacetic acid, mercaptothiazole or the like can be used as a chain. Moving agent. Specific examples of the chain-linking agent, such as a chain-linking agent having a carboxyl group, such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, azlaconic acid, cysteine, ortho-benzoic acid, and derivatives thereof; a chain-shifting agent having a hydroxyl group such as ethyl alcohol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3 - mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(extended ethylene dioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, twelve Alkyl mercaptan, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane thiol, glycerol sulfide, 4,4-sulfurized benzene Mercaptan and the like. In addition, a heterocyclic compound having a mercapto group is used as a chain-shifting agent such as mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2·indolyl-4-methyl-4 -butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylsulfona lactone, 2-mercapto-4-butyl decylamine, N-A Oxy-2-indole-20- 201007356 -4-butylidene, N-methyl-2-mercapto-4-butylidene, N-ethyl-2-nonyl-4-butene Indoleamine, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2-mercapto-4-butylidene , 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalamine, N-ethyl-2-mercapto -5-valeroinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentalinamide, N-(2-ethoxy)ethyl-2-mercapto-5 - Valdecylamine and 2-mercapto-6-caprolactam and the like. φ is a heterocyclic compound having a mercapto group which is not detrimental to the developability of the photocurable resin composition, and is a mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain-linking agents may be used singly or in combination of two or more. (D) Compound having two or more ethylenically unsaturated groups in the molecule The compound having two or more ethylenically unsaturated groups in the fractional φ used in the photocurable resin composition used in the present invention ( D) Photocuring by irradiation with an active energy ray to make the carboxyl group-containing resin (B) insoluble in an aqueous alkali solution or to promote insolubilization. a diacrylate of a diol of such a compound as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, hydroxyethyl a polyvalent acrylate such as an isocyanate or the like, or an oxyethylene adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, and phenolic ethylene oxide a polyvalent acrylate such as an adduct or a propylene oxide adduct; glycerol dicyclo-21 - 201007356 oxypropyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, a polyvalent acrylate of a glycidyl ether such as trisepoxypropyl isocyanate; and a melamine acrylate; and/or a methacrylate corresponding to the above acrylate. Further, for example, a polyfunctional epoxy resin such as a cresol novolac resin epoxy resin or an epoxy acrylate resin which reacts with acrylic acid, or a hydroxyl group of an epoxy acrylate resin and pentaerythritol triacrylate or the like can be used. An epoxy group hydroxyethyl carbamate compound obtained by reacting a hydroxy acrylate with an ethyl melamine compound of a diisocyanate such as an isocyanate. The epoxy acrylate-based resin does not lower the dryness of the touch and can improve the photocurability. The compounding amount of the compound (D) having two or more ethylenically unsaturated groups in the molecule is from 5 to 100 parts by mass, preferably from 1 to 70, based on 100 parts by mass of the carboxyl group-containing resin (B). Parts by mass. When the amount of the above-mentioned compound is less than 5 parts by mass, the photocurability is lowered, and the development of the ruthenium after irradiation with the active energy ray is difficult to form a pattern, which is not desirable. On the other hand, when it is more than 100 parts by mass, the solubility of the aqueous alkali solution is lowered, and the coating film becomes brittle, so that it is not desirable. (E) Thermosetting component In the photocurable resin composition of the present invention, a thermosetting component (E) may be added in order to impart heat resistance. The thermosetting component to be used in the present invention may be an amine resin such as melamine resin or benzoguanamine, or a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, 22-201007356, a compound having two or more cyclic ether groups and/or cyclic thioether groups in the molecule, such as a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxirane compound, or an epirubic ether resin, and a melamine derivative. Or a conventional thermosetting resin such as an amine resin such as a benzoguanamine derivative, a carbonyl diinimide resin, a bismaleimide or a polyoxazoline compound. These may be used alone or in combination of two or more. More preferably, the thermosetting component (E) is a thermosetting compound having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group) in the molecule. The thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having a 3, 4, or 5 carbon ring in the molecule, or a cyclic thioether group. Any one of the compounds having two or more of the two groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxide (E-1) having at least two or more in the molecule The compound of the oxetanyl group, that is, the polyfunctional oxetane compound (E-2), the compound having two or more thioether groups in the molecule, that is, the episulfide resin (E-3). The above polyfunctional epoxy compound (E-1), for example, JER828, JER834, JER1001, JER1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, and Edolon 2055 manufactured by Dainippon Ink and Chemicals Co., Ltd. Epotot YD-011, YD-013, YD-127, YD-128, DER·317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., ar aldite 6 0 71 from Ciba · Specialty Chemicals , araldite6084, araldite GY250, araldite GY260, Sumitomo -23- 201007356 Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, manufactured by Asahi Kasei Industrial Co., Ltd. AER661, AER664, etc. (both trade names) bisphenol A epoxy resin; YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon 165, Epotot manufactured by Dongdu Chemical Co., Ltd. YDB-400, YDB-500, DE ·R · 5 42 by Dow Chemical Co., Ltd., Araldite 8011 from Ciba. Specialty · Chemicals, Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ESB-400, ESB-700, AER 711, AER714, etc. (all are trade names) brominated epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; JER 152, JER154, manufactured by Nippon Epoxy Co., Ltd. DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclon N-730, Epiclon N-770, Epiclon-865 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epotot YDCN-701, YDCN-704, Ciba · Specialty manufactured by Dongdu Chemical Co., Ltd. · Chemicals company's araldite ECN 1 23 5 , araldite ECN1 273 , araldite ECN1299 , araldite XPY3 0 7. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X manufactured by Industrial Co., Ltd., ES CN-2202, AER ECN-235, ECN-299, etc. (all are trade names) made of Asahi Kasei Kogyo Co., Ltd. Epiclon 83 0 manufactured by Industrial Co., Ltd. JER807 manufactured by Nippon Epoxy Co., Ltd., Epotot YDF-170, YDF-175, YDF-200 1, YDF-2004, Ciba · Specialty manufactured by Dongdu Chemical Co., Ltd. araldite 20100735 by Chemicals 6 XPY3 06 (all are trade names) bisphenol F-type epoxy resin; Epotot ST-2004, ST-2007, ST-3000 (trade name) made by Dongdu Chemical Co., Ltd. JER604 manufactured by Epoxy Epoxy Co., Ltd., Epotot YH-434 manufactured by Dongdu Chemical Co., Ltd., araldite MY720 from Ciba · Specialty. Chemicals, and Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all are trade names) Epoxy propylamine type epoxy resin; acetylene-type epoxy resin type epoxy resin such as araldite CY-350 (trade name) of Ciba Specialty Chemicals Co., Ltd.; Celoxide 202 manufactured by Daicel Chemical Industry Co., Ltd., Ciba Chemicals company's aralditeCY175, CY 179, etc. (all trade names) alicyclic epoxy resin; YL-933 made by Japan Epoxy Resin Co., Ltd., TEN, EPPN-501 'EPPN-502 manufactured by Dow Chemical Co., Ltd. Etc. (all of the trade names) of trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin Co., Ltd. 丫 1-6056, 丫 -4 000, YL-6 121 (all are trade names), etc. Cresol or bisphenol epoxy resin or such EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-3 0 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-15 14 (trade name) manufactured by Otsuka Ink Chemical Industry Co., Ltd.; Japan Epoxy resin company's JER157S (trade name) and other bisphenol A / novolac resin epoxy resin; Japan Epoxy resin company YL-931, Ciba. Specialty · Chemicals company araldite 163, etc. (all products Name) tetraphenyl fluorene-based epoxy resin; arbide PT810 from Ciba. Specialty. Chemicals, TEPIC from Nissan Chemical Industries Co., Ltd. (all are trade names), heterocyclic epoxy resin; 25-201007356 Di-epoxy propyl phthalate resin such as Blenmer DGT, etc.; tetra-epoxypropyl dimethyl phenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN manufactured by Nippon Steel Chemical Co., Ltd. -190, ESN-360, epoxy resin containing naphthalene group such as HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; HP-7200, HP-7200H, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin with dicyclopentadiene structure Epoxy propylene chicken methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc., and copolymerized epoxy of cyclohexylmaleimide and epoxypropyl methacrylate Resin; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-45 0 manufactured by Dongdu Chemical Co., Ltd.) ), etc., are not subject to these restrictions. These epoxy resins may be used singly or in combination of two or more kinds. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable. The above polyfunctional oxetane compound (E-2 ) 'e.g. bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-) 3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, I,4- Bis[(3-ethyl-3.oxetanylmethoxy)methyl]benzene, (3-methyl-3.oxetanyl)methacrylate, (3·ethyl- 3-oxetanyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl) a methyl methacrylate or a polyfunctional oxetane such as an oligomer or a copolymer thereof, and an oxetane and a phenol varnish -26- 201007356 resin, poly(P-hydroxyl) An ether compound of a resin having a hydroxyl group such as styrene), a card type bisphenol, a calixarene, a cup-containing resorcinol aromatic hydrocarbon or a sesquioxanes. Other examples are, for example, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. For the compound (E-3) having two or more cyclic thioether groups in the molecule, for example, a bisphenol A-type thioether resin YL7000 manufactured by Nippon Epoxy Co., Ltd. or the like can be used. Further, the epoxy group of the novolac type epoxy resin is substituted with a sulfur atom of a sulfur atom or the like. The amount of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is a cyclic (thio)ether group with respect to 1 part of the carboxyl group of the carboxyl group-containing resin (B). It is preferably 0.6 to 2.5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the cured film, and heat resistance and alkali resistance are lowered. Electrical insulation, etc., it is not an attempt. On the other hand, when it is more than 2.5 equivalents, since a low molecular weight cyclic (thio)ether group remains in the dried coating film, the strength of the coating film is lowered, which is not desirable. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, for example, a compound having two or more isocyanate groups in one molecule (that is, a polyisocyanate compound) or having one molecule A compound of two or more blocked isocyanate groups (that is, a blocked isocyanate compound). As the above polyisocyanate compound, for example, an aromatic polyisocyanate 'aliphatic polyisocyanate or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanide-27-201007356 acid ester, such as 4,4'-diphenylmethane diisocyanate, 2,4-methylphenyl diisocyanate, 2,6-methylphenyl diisocyanate, Naphthalene-1,5-diisocyanate, fluorene-phenyldimethyl diisocyanate, benzodimethyl diisocyanate and 2,4-methylphenyl dimer. Specific examples of the aliphatic polyisocyanate are, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl) Isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate are, for example, dicycloheptane triisocyanate. Further, for example, an adduct of an isocyanate compound, a biuret, and an isocyanate as exemplified above. The blocked isocyanate group contained in the blocked isocyanate compound is protected by reaction of an isocyanate group with a block agent to form an inertized group. When heated to a predetermined temperature, the block agent dissociates to form an isocyanate group 异 block isocyanate compound, and an addition reaction product of an isocyanate chelating block and an isocyanate block agent is used. The isocyanate compound obtained by the reaction with a block agent is, for example, an isocyanate type, a biuret type, addition molding or the like. The isocyanate compound is, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate are, for example, 4,4'-diphenylmethane diisocyanate, 2,4-methylphenyl diisocyanate, 2,6-methylphenyl diisocyanate, naphthalene-1,5-di Isocyanate, phthalic acid dimethyl dimethyl diisocyanate, m- benzene dimethyl diisocyanate and 2,4. methylphenyl dimer. Specific examples of the aliphatic polyisocyanate are, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl) Isocyanate) -28- 201007356 and isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate. Isocyanate block agents such as phenolic blockers such as phenol, cresol, xylenol, chlorinated phenol and ethyl phenol; ε-caprolactam, δ-valeroguanamine, β-propionamide, etc. a guanamine blocker; an active methylene blocker such as ethyl acetoxyacetate or acetonitrile; (methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl) Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, anisole, methyl glycolate, butyl glycolate, diacetone alcohol, An alcohol-based block agent such as methyl lactate or ethyl lactate; a quinone blocker such as formaldehyde hydrazine, acetaldehyde oxime, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine or cyclohexane hydrazine; a thiol blocker such as butyl mercaptan, hexyl mercaptan, butyl thiol, thiophene, methyl thiophene or ethyl thiophene; acid amide amine such as decylamine or benzoguanamine Blocking agent; sulfonium imide succinate and sulfonium imide maleate; amine blocker such as xylidine, aniline, butylamine, dibutylamine; imidazoline, 2-ethyl An imidazoline blocker such as imidazoline; an imine blocker such as methyleneimine or propylimine, etc. The blocked isocyanate compound is commercially available, for example, Sumijur BL3175, BL-4165, BL-1100, BL-1 265, Desmojur TPLS-2957 'TPLS-2062, TPLS-2078, TPLS-2117, Desmosamu 2170, desmosamu 2265 (above is Sumitomo Bayer urethane, trade name), Coronato 2512, Coronato 2513, Coronato 2520 (above is made by Japan Polyurethane Industrial Co., Ltd.), B-830, B-815, B-846, B-870 « B-874, B-882 (Mitsui Takeda -29- 201007356

Chemical company, trade name), ΤΡΑ-Β 80E, 17B-60PX, E402-B80T (made by Asahi Kasei Chemicals Co., Ltd., trade name). Further, Sumijur BL-3175 and BL-4265 can be obtained by using methyl acetonitrile as a block agent. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more. The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 1 part by mass based on 1 part by mass of the carboxyl group-containing resin. Preferably, it is 2 to 70 parts by mass. When the amount of the above-mentioned compounding amount is less than 1 part by mass, the strong toughness of the coating film cannot be obtained, and therefore it is not desired. On the other hand, when it is more than 100 parts by mass, the storage stability is lowered, so it is not desirable. Specific examples of the above-mentioned amine-based resin such as a melamine derivative or a benzoguanamine derivative, such as a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol urea-based compound, and Hydroxymethyl urea compound and the like. In addition, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycol urea compounds and alkoxymethylated urea compounds are A hydroxymethyl group obtained by converting a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol ureido compound, and a methylol urea compound into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. In particular, a melamine derivative having a hormone concentration of 0.2% or less which is excellent in human body or environment is preferable. Such commercial products such as Cymel 300, same 301, same as 3 03, same as 201007356 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 23, the same 1141, the same 272' with 202, the same 1156, the same 1158, the same 1123' with 1170, the same 1174, the same UFR65, the same 00 (above is Mitsui Cyanamide (share) system), Nikarak Mx-75 0, the same Mx-032, the same Mx-270, the same Mx- 280 ' with Mx-290, with Mx-706, with Mx-708, with Mx-40, with Mx-31, with Ms-11, with Mw-30, with Mw-30HM, with Mw-390, with Mw- 100LM, same as Mw-750LM (above is the three and chemical system). These thermosetting components may be used singly or in combination of two or more kinds. When the above-mentioned thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalyst such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-fluoroethylethyl- Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide; benzyldimethylamine, 4-(II) Methylamino)-indole, indole-dimethylbenzylamine, 4-methoxy-indole, indole-dimethylbenzylamine, 4-methyl-indole, indole-dimethylbenzyl An amine compound such as a base amine, a bisamine compound such as adipic acid diamine or azelaic acid diamine; a phosphorus compound such as triphenylphosphine or the like. In addition, the marketer is, for example, 2ΜΖ-Α, 2ΜΖ-0Κ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (both trade names of imidazole compounds) manufactured by Shikoku Chemical Industrial Co., Ltd., and U-CAT (registered trademark) manufactured by San-apro Co., Ltd. 3 5 03N, U-CAT 3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CAT SA102, U-CAT 5 002 (all are bicyclic guanidine compounds and their salts )Wait. There is no particular limitation -31 - 201007356, as long as it is a thermosetting catalyst for epoxy resin or oxetane compound, or can promote the reaction of epoxy group and / or oxetane with carboxyl group, Separately or in combination of two or more. Moreover, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2- Vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine•isocyanate adduct, 2,4-diamino-6 - an S-triazine derivative such as a methacryloxyethyloxy-S-triazine/isocyanate addition product, preferably a compound which can also function as an adhesion imparting agent and the above heat Hardening catalyst. The amount of such a thermosetting catalyst is sufficient in a ratio of a general amount, for example, relative to 1 part by mass of the carboxyl group-containing resin (B) or a heat having two or more cyclic (thio)ether groups in the molecule. The curable component (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. In the photocurable resin composition of the present invention, in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate, a adhesion promoting agent can be used. Specifically, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl-1- Phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetra An azole, a benzotriazole, a carboxybenzotriazole, an amine group-containing benzotriazole, a decane coupling agent, and the like. The photocurable resin composition of the present invention can be blended with a colorant. As the coloring agent, a conventional coloring agent such as red, blue, green or yellow may be used, and a pigment, a dye or a pigment may also be used. In terms of reducing environmental load and affecting the human body, it is preferred to be halogen-free. -32- 201007356 Blue coloring agent: Blue coloring agents are alizarins and lanthanides, and pigments are compounds classified as pigments, specifically, for example, the following color index (CI; The Issued by Society of Dyers and Colourists No.; 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 ginseng dyes can be used with 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 more. In addition to the above, a halogen-substituted or unsubstituted alizarin compound can also be used. Green colorants: Green colorants are similarly alizarin, lanthanide, and lanthanide, specifically, such as Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. . In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used. Yellow coloring agent: yellow coloring agent is monoazo type, bisazo type, condensed azo type, benzene-33-201007356 and imidazolidinone type, isoindolinone type, hydrazine type, etc., specifically, for example, the following By. Onion _ system: S ο 1 vent Y e 11 〇w 1 6 3, P igmentye 11 〇w 2 4, Pigment yellow 108, Pigment yellow 193, Pigment yellow 147, Pigment yellow 199, Pigment yellow 202 ° different B ketone Line: Pigment yellow 110, Pigment yellow 109, Pigment yellow 139, Pigment yellow 179, Pigment yellow 185.

Condensed azo system: Pigment yellow 93, Pigment yellow 94, Pigment yellow 95, Pigment yellow 128, Pigment yellow 155, Pigment yellow 166 ' Pigment yellow 180 ° Benzymidone series: Pigment yellow 120, Pigment yellow 151, Pigment yellow 154, Pigment yellow 156, Pigment yellow 175, Pigment yellow 181 ° Monoazo system: Pigment yellow 1,2,3,4,5,6,9,10,12,61, 62,62 : 1,65,73 , 74,75,97,1 00,1 04,1 05,1 1 1,1 1 6,1 67,1 68, 169,182,183. The bisazo system: Pigment yellow 1 2,1 3,1 4,1 6,1 7,5 5,63, 81,83,87,126,127,152,170,172,174,176,188,198. Red coloring agent: Red coloring agent is monoazo type, disazo type, azo compound type, benzimidazolone type, lanthanide type, ketal pyrrolopyrrole type, condensed azo system, lanthanide series, quinine An anthrone or the like is specifically, for example, the following. -34- 201007356 Single azo 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° Azo system: Pigment red 37, 38, 41. Monoazo compound 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.

Benzymidone: Pigment red 171, Pigment red 175, Pigment red 176, Pigment red 185, Pigment red 208 ° Philippine: Solvent red 135, Solvent red 179, Pigment red 12 3, Pigment red 149, Pigment red 166 , Pigment red 17 8, Pigment red 179, Pigment red 190, Pigment red 194, Pigment red 224. The ketal oxime ratio is slightly smaller than the ratio: Pigment red 254, Pigment red 25 5, Pigment red 264, Pigment red 270, Pigment red 272 ° condensed azo system: Pigment red 220, Pigment red 144, Pigment red 166, Pigment red 214, Pigment red 220, Pigment red 221, Pigment red 242 ° 恵醌: P igmentred 1 6 8, P igmentred 1 7 7, Pigment red 216, Solvent red 149, Solvent red 150,

Solvent red 52, So1vent red 207 ° Salivation V ketone system: P i g m e n t r e d 1 2 2, P i g m e n t r e d 2 0 2

Pigment red 206, Pigment red 207, Pigment red 209 ° -35- 201007356 Others For the purpose of adjusting the color tone, a coloring agent such as purple, orange, color or black may be added. Tea specifics such as Pigment Violet 19, 23, 29, 32, 36 > 38, 42 , Solvent Violet 1 3 ' 36, CIPigment Orange 1 , CIPigment Orange 5 , C. I. Pi gment Orange 1 3 , CIPigment Orange 14, CIPigment Orange 16 C.I.Pigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36 CIPigment Orange 38, C.I.Pigment Orange 40, C.I.Pigment Orange 43, CI Pigment Orange 46, CIPigment Orange 49, CIPigment Orange 5 1 , C.I.Pigment Orange 61, CIPigment Orange 63 C.I.Pigment Orange 64, CIPigment Orange 71, C.I.Pigment Orange 73, CIPigment Brown 23,

C.I. Pigment Brown 25 'C.I. Pigment Black 1, C.I. Pigment Black7, etc. The mixing ratio of the coloring agent is not particularly limited, and is preferably from 0 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). , is full. When most of the polymer materials are oxidized, the chain oxidation is deteriorated, and the function of the polymer material is lowered. Therefore, in the photocurable resin composition of the present invention, in order to prevent oxidation, it is possible to add (1) a free radical make-up agent which invalidates the generated radicals and/or (2) decomposes the produced peroxide into a harmless substance, and does not produce a new peroxide------------ An antioxidant such as a decomposing agent. As an antioxidant of a radical-filling agent, specific compounds such as hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di- 3-butyl-P-cresol, 2,2-methylene-bis-(4-methyl-6-tert-butylphenol), 1,1,3-parade (2-methyl-4) _hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-3-butyl-4-hydroxybenzene Methyl)benzene, 1,3,5-gin (3',5'-di-3-butyl-4-hydroxybenzyl)-3-triazine-2,4,6-(111,311,51 a benzophenone compound such as phenol, benzophenone or p-benzophenone such as ninhydrin, bis(2,2,6,6-tetramethyl-4-piperidyl)-decanoate or phenothiazine An amine-based compound, etc. The radical-filling agent may also be a commercially available product such as Adekatab AO-30, Adekatab AO-330, Adekatab AO-20, Adekatab LA-7 7, Adekatab LA-57, Adekatab LA -67, Adekatab LA-68, Adekatab LA-87 (above is manufactured by Asahi Kasei Co., Ltd.) 'IRGANOX 1010, IRGANOX 1 03 5 IRGANOX 1 076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TI NUVIN 5100 (the above is a product of Ciba. Specialty. Chemicals, trade name), etc. As an antioxidant of a peroxidizing agent, a specific compound such as a phosphorus compound such as triphenylphosphorus or a pentaerythritol tetralauryl sulphonate A sulfur-based compound such as dilauryl sulfide dipropionate or distearyl 3,3'-thiodipropionate.

The peroxide decomposing agent may be a commercially available product, for example, Adekatab TPP-37-201007356 (made by Asahi Kasei Co., Ltd., trade name), Mac AO-412S (made by Adeka Agars Chemical Co., Ltd., trade name), Sumilizer TPS (Sumitomo Chemical system, trade name), etc. The above-mentioned antioxidants may be used alone or in combination of two or more. When the polymer material absorbs light, it causes decomposition and deterioration. When the photocurable resin composition of the present invention is used for the stabilization of ultraviolet rays, an ultraviolet absorber can be used in addition to the above antioxidant. The ultraviolet absorber such as a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an amine anisate derivative, Dibenzoylmethane derivatives and the like. Specific benzophenone derivatives 'eg 2_transalkyl-4_methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2·hydroxy-n-octyloxybenzophenone Ketone, 2,2,-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, etc.; specific benzoic acid vinegar derivatives such as 2-ethylhexyl salicylate , phenyl salicylate, P - 3 - butyl phenyl salicylate, 2, 4-di- 3 - butyl phenyl - 3, 5 · di - 3 - butyl -4- Mercaptobenzoic acid vinegar and cetyl-3,5-di-3-butyl-4-hydroxybenzoate; etc.; specific examples of benzotriazole derivatives, such as 2- (2'- Hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2,-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3,- 3 -butyl-5'-methylphenyl)-5-chlorinated benzotriazine, 2_( 2'-hydroxy-3,5,-di-3-butylphenyl)-5- Benzotriazole chloride, 2-(2, hydroxy-5,-methylphenyl)benzotriazole and 2-(2'-hydroxy-3, '5'-di-3-butyl-amine Phenyl phenyl) benzotriazole; examples of specific triazine derivatives such as hydroxyphenyltriazine, bisethylhexyloxybenzene Methoxy triazine. -38- 201007356 The UV absorbers are also commercially available, such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460 , TINUVIN 479 (above is Ciba ♦ Specialty. Chemicals company, trade name) and so on. The above-mentioned ultraviolet absorbing agent may be used singly or in combination of two or more kinds, and the molded article obtained from the photocurable tree φ lipid composition of the present invention can be stabilized by using the above-mentioned antioxidant. The photocurable resin composition of the present invention can be blended with a chelating agent in order to improve the physical strength of the coating film and the like. The chelating agent may be at least one selected from the group consisting of conventional inorganic chelating agents and organic hydrazines, preferably using inorganic cerium filling agents, particularly barium sulfate, spherical cerium oxide and talc. Alternatively, titanium oxide may be added as a white chelating agent as a white photoresist. These chelating agents may be used alone or in combination of two or more. The amount of the above-mentioned chelating agent is preferably 300 parts by mass or less, more preferably 〇_1 to 30,000 parts by mass, per 100 parts by mass of the resin (B) containing the carboxyl group φ, and most preferably 〇1 to 30,000 parts by mass. 〇·1~150 parts by mass. When the amount of the chelating agent is more than 300 parts by mass, the viscosity of the photocurable resin composition becomes high, the printability is lowered, and the cured product becomes brittle, so that it is not desirable. Further, when the photocurable resin composition of the present invention is used for synthesizing the carboxyl group-containing resin (B) or a composition, or when applying a viscosity to a substrate or a negative film, an organic solvent can be used. The organic solvent is, for example, a ketone, an aromatic hydrocarbon, a glycol ether, an ethylene glycol ether acetate, an ester, an alcohol, an aliphatic hydrocarbon, a petroleum solvent, or the like -39-201007356. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbitol , glycol carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate Dipropylene glycol

Esters such as alcohol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, and solvent A petroleum solvent such as oil. The organic solvent may be used singly or in combination of two or more.

The photocurable resin composition of the present invention may contain a conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, butyl catechol, pyrophenol, phenothiazine or the like as required. , known as tackifiers, lanthanum, fluorine, polymer, etc., antifoaming agents and/or leveling agents, imidazole, thiazole, triazole, etc., such as fine powder of cerium oxide, organic bentonite, and montmorillonite. A conventional additive such as a decane coupling agent, an antioxidant, or a rust inhibitor. The above thermal polymerization inhibiting agent prevents the use of the polymerizable polymer for thermal polymerization or polymerization over time. The thermal polymerization inhibiting agent is, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, 3-butyl catechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy 2-Hydroxybenzophenone, copper chloride, phenothiazine, proguanil, naphthylamine, anthraquinone-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2' - methylene bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactants, Methyl salicylate, phenothiazine, nitroso compound-40-201007356, chelating agent of nitroso compound and A1, and the like. The photocurable resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer formed of the photocurable resin composition formed on the carrier film. In the case of dry film formation, the photocurable resin composition of the present invention can be diluted with the above organic solvent to adjust to an appropriate viscosity, and by an upright applicator, a blade coater, a slit coater, a rod Applicator, extrusion applicator 0, reversible applicator, drive roll applicator, gravure coater, spray applicator, etc., coated on the load-bearing film in a uniform thickness, usually The film was dried by drying at a temperature of 50 to 130 ° C for 1 to 3 minutes. The coating film thickness is not particularly limited, and is generally suitably selected from the range of 1 to 150 μm, preferably 20 to 60 μm, after drying. A plastic film may be used for the negative film, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like may be used. . The thickness of φ of the negative-loading film is not particularly limited, and is generally suitably selected from the range of 10 to 150 μm. After the film formation on the carrier film and the purpose of preventing dust from adhering to the surface of the film, it is preferable to laminate a peelable surface film on the film surface. For the peelable surface film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the surface film is peeled off, the adhesion between the film and the surface film is higher than that of the film and the carrier film. Smaller. Further, the photocurable resin composition of the present invention or the dry film, -41 - 201007356, is cured by photohardening on copper. Photohardening can also be achieved by means of UV exposure, but it can also be hardened by laser light with a wavelength of 3 50 to 41 Onm. Specifically, a dry film, a cured product, and a printed circuit board are formed as follows. In other words, the photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method by the above organic solvent, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or a sieve. A method such as a screen printing method, a curtain coating method, or the like is applied to a substrate, and is carried out at about 60 to 100. (At the temperature: 'The organic solvent contained in the composition is volatilized and dried (false drying) to form a wrinkle-free coating film. Further, the above composition is applied onto the carrier film' and dried. After the film is formed and the photocurable resin composition layer is applied to the substrate in contact with the substrate, the resin insulating layer can be formed by peeling off the negative film. Then, by contact (or non-contact method) The patterned photomask is selectively exposed by an active energy ray, and the unexposed portion is developed by a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a photoresist pattern. Further, the thermosetting component is contained ( In the case of the composition of E), for example, the carboxyl group of the carboxyl group-containing resin (B) and the cyclic ether having two or more molecules in the molecule can be thermally cured by heating at a temperature of about 140 to 18 (TC). The thermosetting component (E) of the group and/or the cyclic thioether group is reacted to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Contains thermosetting In the case of (E), thermal radical polymerization is carried out by heat treatment, and the ethylenically unsaturated bond remaining in the unreacted state during exposure is subjected to thermal radical polymerization, and when the film properties are improved, it may be carried out depending on the purpose and use. 201007356 Heat treatment (thermosetting). In addition to the printed circuit board or flexible printed circuit board on which the circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass can be used. - Polyimide, glass cloth / non-woven fabric - epoxy tree, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluorine resin, polyethylene · PPO. Cyanate ester and other composite materials a copper-clad laminate, a styrene film, a PET film, a glass substrate, a φ ceramic substrate, a wafer plate, etc. of a grade (FR-4, etc.), and a volatilization drying after coating the photocurable resin composition of the present invention A hot air circulation type drying furnace, an IR furnace, a hot plate, a conveyor belt oven, etc. (using a heat source having a heating method by steam, a method of bringing a hot air in the dryer into contact with the flow, or a nozzle by using a nozzle Blowing on the branch In the above, the photocurable resin composition of the present invention is applied and volatilized and dried, and then the obtained coating film is subjected to exposure (irradiation of active energy ray φ). The exposure unit (the portion irradiated by the active energy ray) is cured. The exposure machine used for the active energy ray irradiation can be a laser direct drawing device (laser direct developing device) or a metal halide lamp. An exposure machine, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury-illuminated arc lamp, or a direct drawing device using an ultraviolet lamp such as a (ultra) high-pressure mercury lamp, and a maximum wavelength of 350 to 410 nm is used. When the laser light is used as the active energy ray, it may be any one of a gas laser and a solid laser. Further, the exposure amount varies depending on the thickness of the film, and is generally 5 to 200 mJ/cm 2 in the case of -43 to 201007356, preferably. The ratio is 5 to 100 m J/cm 2 , and more preferably 5 to 50 mJ/cm 2 . The direct drawing device may be, for example, a device manufactured by Orbotech Co., Ltd., a Pentax company, or the like, as long as it can oscillate laser light having a maximum wavelength of 350 to 4 l 〇 nm. The developing method may be a dipping method, a rinsing method, a spraying method, a brushing method, or the like, and the developing solution may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonium water or an amine. An aqueous solution of the base. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited by the following Examples. In addition, in the following "parts" and "%", there are no special restrictions, all based on quality. [Examples] Resin Synthesis Example 1 070 g (epoxypropyl number (total aromatic ring): 5.0 mol) o-cresol novolac resin type epoxy resin was added to 600 g of diethylene glycol monoethyl ether acetate [Great Japan Ink Chemical Industry Co., Ltd., EPIC LON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6], 360 g (5.0 mol) acrylic acid, and 1.5 g hydroquinone at 100 ° C Heat and stir and dissolve evenly. Then, 4.3 g of triphenylphosphine was added, and the mixture was heated at U 〇 ° C to carry out a reaction for 2 hours, and then the temperature was raised to 120 ° C and the reaction was carried out for 12 hours. To the obtained reaction liquid, 4 15 g of aromatic hydrocarbon (Solvellso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, and -44 - 201007356 was reacted at no t: for 4 hours, and cooled. After that, a resin solution having a solid content of 89 mg KOH/g and a solid content of 65% was obtained. This material is referred to as a resin solution B-1 varnish. The above carboxyl group-containing resin is as described (6). Examples 1 to 8 and Comparative Examples 1 and 2 The components shown in the following Table 1 were blended in the proportions (mass parts) shown in Table 1, and premixed with a stirrer, and then kneaded by three roll mills to prepare a solder resist. A photocurable resin composition is used. Here, the dispersion of the obtained photocurable resin composition was evaluated by particle size measurement by a pellet measuring instrument manufactured by Erichs En Co., and any composition was 15 μm or less. Further, Comparative Examples 1 and 2 are examples in which the cellulose derivative used in the present invention is not blended. -45- 201007356 [Table 1] Composition (parts by mass) Reality m Comparative Example 1 2 3 4 5 6 7 8 1 2 A component (Α·1)*1 50 (Α-2)*2 — 50 (Α· 3)*3 50 (A-4)* 4 50 CA-5)*S 50 (Α·6)*6 50 — (A-7)*7 50 — One (A-8)*8 — — — — — .” — 50 — — B组成ίΒ-1) 155 155 155 155 155 155 15 5 155 155 155 Phenoxy resin “paint*9 50 C component (Cl)*10 1 1 1 1 1 1 1 1 1 1 (C-2)*ll 5 5 5 5 5 5 5 5 5 5 D component (Dl)*12 20 20 20 20 20 20 20 20 20 20 (D-2)*13 10 10 10 10 10 10 10 10 10 10 ΕIngredients (El)*14 15 15 15 15 15 15 15 15 15 15 (E-2)*15 25 25 25 25 25 25 25 25 25 25 Test Catalyst ^ Melamine 3 3 3 3 3 3 3 3 3 3 Colorant*16 0.3 0.3 0.3 0.3 0.3 0V3 0.3 0.3 0.3 0.3 Colorant*17 0.8 0.8 0.8 0.8 0.8 0.8 08 0.8 0.8 0.8 Colorant*18 100 100 100 100 100 100 100 100 100 100 Antimony Defoamer 3 3 3 3 3 3 3 3 3 3 Organic solvent DPM*19 20 one

The components in the above Table 1 are shown in detail in Table 2 below. G -46- 201007356 [Table 2]

*1 CAB · 55b 0.01 manufactured by EASTMAN Co., Ltd. (Ethyl mercapto content: 2.0 wt%, butyl sulfonate content: 53.0 wt%, hydroxyl content: 15 wt%, Tg: 85. 〇, mW16,000) 20 wt% DPM solution * 2 EASTMAN CAB . 55 Bu 0.2 (Ethylene sulfonate content: 2.0 wt ° /., butyl sulfonate content: 52.0 wt%, hydroxyl content: 18 wt%, Tg: 101 乞, MW 30,000) 20 wt% DPM solution * 3 EASTMAN company CAB. 553 . 0.4 (acetonitrile content: 2.0 wt%, butyl sulfonate content: 46.0 wt%, hydroxyl content·_ 4, 8 wt%, Tg: 136. (: 'MW 20,000) 20 wt% DPM solution *4 CAB made by EASTMAN. 500 · 5 (ethyl ketone content: 4.0 wt%, butyl sulfonate content: 51 _0 wt%, hydroxyl content: LO wt%, Tg: 96. (:, M_W. 57,000) 20 wt% DPM solution * 5 CAB · 381 by EASTMAN Co., Ltd. 〇 ·5 (Ethyl thiol content: 13.5 wt%, butyl sulfonate content: 38.0 wt%, hydroxyl content: i. 3 wt%, Tg: 130 ° C, M. W 30,000) 20 wt% DPM solution * 6 CAP manufactured by EASTMAN. 504 . 0.2 (acetonitrile content: 0.6 wt0 / fluorene, propylene group content: 42.5 wt%, hydroxyl content: 5 〇 wt%, Tg: 159 ° C, M. W15,000) 20 wt% DPM solution * 7 EASTMAN company CAP · 482 0.5 (acetonitrile content: 2.5 wt%, propylene group content: 45.0 wt%, hydroxyl content: 2.6 wt ° / 〇, Tg: 142 ° C, MW 25,000) 20 wt% DPM solution preparation * 8 manufactured by EASTMAN CAP · 482 · 20 (acetonitrile content: 2.5 wt%, propylene group content: 46.0 wt%, hydroxyl content: 1.8 wt%, Tg: 147 ° C, MW 75,000) 20 wt% DPM solution * 9 phenoxy Resin (Dongdu Chemical Co., Ltd.) YP-50, Tg: 10 (TC, MW14200) 20wt% CA solution no 2-(ethyloxyiminomethyl) thioxanthene-9-one*11 2-A Base-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one*12 dipentaerythritol hexaacrylate (DPHA; manufactured by Nippon Kayaku Co., Ltd.) *13 Trimethylolpropane Triacrylate (TMPTA; manufactured by Nippon Kayaku Co., Ltd.) *14 phenol novolac type epoxy resin (DEN438; manufactured by Dow Chemical Co., Ltd.) *15 dixylenol type epoxy resin (YX-4000; Japan epoxy resin) (Unit) system *16 CI Pigment Blue 15 : 3 *17 CIPigment Yellow 147 *18 Barium sulfate (B-30: manufactured by Hashi Chemical Co., Ltd.) *19 Dipropylene glycol monomethyl ether-47- 201007356 Performance evaluation = <Sensitivity> Copper β-based film with a film thickness of 35 μm After washing WH jet mill, to be washed with water, dried, and coated by screen printing method tables photocurable resin composition described in 1, and dried for 30 minutes at 80 ° C of a hot air circulation type drying oven. After drying, exposure was carried out through a trapezoidal plate (Kodak No. 2) at an exposure amount of 50 mJ/cm 2 , and a residual solution of sodium carbonate at 30° C. was used for development for 60 seconds at a spray pressure of 2 MPa. The number of segments of the trapezoidal plate was evaluated as the sensitivity. <Touch-drying property> Each of the photocurable resin compositions described in Table 1 was applied by screen printing to a copper foil substrate having a pattern, and dried in a hot air circulating drying oven at 80 °C. Leave it to room temperature for 30 minutes. A negative film made of PET was placed on the substrate, and a pressure-melting treatment was carried out under reduced pressure for 1 minute using an ORC company (HMW-GW20). Then, the film was attached to the negative film. ◎: When peeling off the film, there is no resistance at all, and there is no trace on the coating film. When the film is peeled off, there is no resistance at all, but there is a slight trace on the coating film. △: When the film is peeled off, only the tip is resistant, and the coating is applied. The film has a slight trace X: when it is peeled off, it is resistant, and there is a clear trace on the coating film <dry management width> -48 - 201007356 The photocurable resin compositions described in Table 1 are each screen-printed. It was applied onto a patterned copper foil substrate and dried in a hot air circulating drying oven at 80 °C. After the start of drying, the substrate was taken out every 10 minutes between 20 minutes and 70 minutes, and allowed to cool off at room temperature. The substrate was developed by using a 1 wt% aqueous sodium carbonate solution at 30 ° C for 20 seconds under a spray pressure of 2 MPa, and the maximum allowable drying time without residue was taken as the dry management width. ❹ <breakpoint> The photocurable resin compositions described in Table 1 were each applied by screen printing onto a patterned copper foil substrate in a hot air circulating drying oven at 80 °C. Dry. After drying, it was allowed to cool to room temperature, and subjected to full exposure treatment at an exposure amount of 50 mJ/cm2. At this time, half of the substrate was shielded from light by a light shielding film. After the exposure, the time necessary for developing the unexposed portion of the substrate (30 ° C, 〇 2 MPa, 1 wt% aqueous sodium carbonate solution) φ was taken as a break point. Characteristic test: Preparation of coating film property evaluation substrate: Each of the photocurable resin compositions described in Table 1 was applied by screen printing to a copper foil substrate on which a pattern was formed, and dried at 80 ° C for 30 minutes. Allow to cool to room temperature. Then, the solder resist pattern was exposed at an exposure amount of 50 mJ/cm 2 , and development treatment (30 ° C, 〇. 2 MPa, 1 wt% aqueous sodium carbonate solution) was carried out to obtain a photoresist pattern. The substrate was heated in a hot air-49-201007356 circulating drying oven at 150 °C for 60 minutes. After hardening, the coating film was evaluated by irradiating ultraviolet rays at 10,000 ml/cm2 in a uv conveyor. Substrate. The following characteristic evaluation test was carried out for the obtained evaluation substrate. <Welding heat resistance> The evaluation substrate coated with the rosin-based flux was immersed in a solder bath at 260 ° C for 60 seconds, and after the flux was washed with the modified alcohol, the tape peeling test was performed to evaluate the photoresist The peeling of the layer. The evaluation criteria are as follows: 〇: no peeling Δ: slight peeling in the circuit X: irrespective of the circuit, total peeling < resistance to electroless gold plating> Electroless nickel plating using a commercially available product on the evaluation substrate The bath and the electroless gold plating bath were subjected to electroplating under conditions of nickel ruthenium.5 μm, gold ruthenium, iridium 3 η η, and visually confirmed whether or not the plating solution was infiltrated, and the peeling of the photoresist layer was evaluated by tape peeling. The evaluation criteria are as follows. 〇: No bleeding or peeling △: No peeling, there is bleeding situation X: There is peeling in the circuit The evaluation results are shown in Table 3. -50 * 201007356 [Table 3] Characteristic example Comparative example 1 2 3 4 5 6 7 8 1 2 Sensitivity (segment) 5 5.5 5 6 6 6 6 6 6 6.5 Rhyme management width (minutes) 60 60 70 60 50 60 60 60 60 20 Finger dryness Δ 〇〇〇〇〇〇. ◎ X 〇 solder heat resistance 〇〇〇〇〇〇◦ 〇〇〇 electroless gold plating resistance 〇〇〇〇〇〇〇〇〇〇 break point (seconds) 42 41 36 33 33 26 28 25 21 120 謇 From the results of the above Table 3, the present invention contains a photocurable resin composition of the cellulose derivative (A), which is compared with a conventional photocurable resin composition. In addition, since the sensitivity, the drying management width, the solder heat resistance, and the resistance to the shovel are not deteriorated, and the dryness after the drying is excellent, there is no need to apply a negative film or the like, and it is extremely useful as a photocurable composition. Further, in the case of Comparative Example 2 containing a phenoxy resin, the dryness of the touch was good, but the drying management width was short, and the developability was also poor. φ A-3 varnish of Table 4 of the cellulose varnish (20% DPM solution of CA-553-0.4 manufactured by EASTMAN Co., Ltd.) was used, and the following formulation was used to form a dispersion in which the pigment was dispersed by bead milling. [Table 4] Blue Dispersion Yellow Dispersion A-3 Varnish 50 50 C 丄 Pigment Blue 15.4 10 CIPigment Yellow 147 10 DPM 40 40 -51 - 201007356 Dispersion conditions were obtained by using a bead mill (Bubler) to make beads YTZ bead diameter: 1mm bead filling rate: 95%, with roller speed; lOOOrpm, discharge amount: 100g/min. Further, the filter having an opening diameter of 5 μm was excessively reduced. The resulting dispersion was allowed to stand at room temperature for more than 1 month without separation. Further, when DJ was used in place of the hydrazine-3 varnish, it was confirmed that the pigment was precipitated within one week, and it was coarse particles of 5 μm or more. Examples 9 to 1 1 and Comparative Example 3 ® Compositions were prepared in accordance with the mixing examples shown in Table 5 below.

-52- 201007356 [^5] Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Formulation Example 5 A component (A-6) 4 0 4 0 4 0 4 0 4 0 B component (B-2) *2〇 155 parts (B-3) *21 155 parts (B-4) * 22 155 parts 77 parts (Β·5) *23 222 parts 111 parts C ingredients 03 氺 24 2 parts 2 parts 2 parts 2 parts 2 parts D ingredients D-1 20 parts 20 parts 20 parts 20 parts 20 parts E ingredients Ε·2 20 parts 20 parts 20 parts 20 parts 10 parts Ε·3 * 25 10 parts 10 parts 20 parts Ε·4 氺26 10 parts 10 parts Ε- 5 *27 5 parts of benzoguanamine 2 parts 1 part 2 parts 2 parts 3 parts melamine 3 parts 3 parts 3 parts 3 parts 3 parts phenothiazine 0. 2 0. 2 0. 2 0. 2 0. 2疏基苯三唑 0. 5 0. 5 0. 5 0. 5 0. 5 Blue Dispersion 3 3 3 3 3 Yellow Disperse Hip 8 8 8 8 8 塡 Charger 5 0 5 0 5 0 5 0 5 0 defoamer 1 1 1 1 1

*20; Nippon Chemical Co., Ltd. ZFR-1401H (solid content 65%) is equivalent to the above-mentioned carboxyl group-containing resin (7) *21; Nippon Chemical Co., Ltd. UTE-3000 (solid content 65%) is equivalent Description of the above-mentioned carboxyl group-containing resin (3) *22; DIC (unit) UE-9210 (solid content: 65%) corresponds to the above-mentioned carboxyl group-containing resin (6) In addition, the addition of the epoxy methacrylate Carboxylic acid reaction of light anti-53- 201007356 acid-modified epoxy acrylate acrylate * 23 ; Daicel Chemical Industry Co., Ltd. Cyclomer P (AC A ) Z250 (solid content 45%) equivalent to the above Description of the carboxy resin (1) *24; OXE-02 *25 manufactured by Ciba Japan Co., Ltd.; methylated methylol melamine III and MW-30 *26 manufactured by Chemical Co., Ltd.; block isocyanate Asahi Kasei Chemicals Co., Ltd. TPA- B-80E (solid content 80%)

*27; Bismaleimide Ke _ Ai Chemical Co., Ltd. BMI The composition of the mixing examples 1 to 5 was dispersed by the bead mill to adjust the coarse particles to ΙΟμηη or less. After the composition was diluted with methyl ethyl ketone, a dry film was produced under the following conditions. <Production of dry film> Each of the photocurable resin compositions having a yttrium-developing type and a thermosetting property was applied to a PET film (R310 manufactured by Mitsubishi Poly" Co., Ltd. using an applicator having a film thickness of 30 μm after drying. : 16μιη), dried at 40~100 °C to make a dry film. <Density Drying Test as Dry Film> The obtained dry film was loaded on a copper-clad laminate having a thickness of 1.6 mm on which the copper surface was polished and honed, and then the same copper was repeatedly laminated thereon. The laminate was placed at 23 ± 2 ° C for 1 hour. Then, the laminated copper-clad laminate and the dry film having a weight of 201007356 were peeled off, and it was confirmed whether or not a dry coating film adhered to the copper surface. (Example 9) The results of the above-mentioned dry touch test were carried out on the dry film produced by using the compositions described in the mixing examples 1 to 5, and all the examples of the mixing were not applied. (Comparative Example 3) The dry film of the component (A) was removed from the composition described in the mixing examples 1 to 5, and as a result of the above-mentioned dry touch test, the part was peeled off from the dry film and posted on the copper surface. . <Production of substrate and coating film characteristics by dry film> After polishing and honing the FR-4 substrate on which the circuit was formed, a true φ-empty layerer (MVLP-500 manufactured by Nihon Seiki Co., Ltd.) was used at 0.8 MPa, 80 The dry film obtained by blending the compositions of Examples 1 to 5 was heated and laminated on the substrate under a condition of 1 C for 1 minute to prepare an evaluation substrate. The obtained evaluation substrate was exposed to a solder resist pattern at the same exposure amount of 50 mJ/cm 2 as described above, and developed (30 ° C, 0.2 MPa, 1 wt% aqueous sodium carbonate solution) to obtain a photoresist pattern. The substrate was heated in a hot air circulating drying oven at 150 ° C for 60 minutes, and then cured, and then irradiated with ultraviolet rays under a condition of 10 μm/cm 2 in a UC transfer furnace to obtain a coating property evaluation substrate. For the obtained evaluation substrate, a characteristic evaluation test of solder heat resistance - 55 - 201007356 and electroless gold plating resistance was performed. As a result, the solder heat resistance of the substrate produced by using the dry film obtained by combining the compositions of Examples 1 to 5 was immersed at 260 ° C for 60 seconds without peeling. The electroless gold plating resistance of the substrate-free sheet produced by using the dry film obtained by blending the compositions of Examples 1 to 5 was not peeled off in the tape peeling test after electroless gold plating.

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Claims (1)

201007356 VII. Patent application scope: 1. A photocurable resin composition characterized by containing a cellulose derivative (A) and a photocurable component. 2. The photocurable resin composition of claim 1, wherein the cellulose derivative (A) is solvent-soluble. 3. The photocurable resin composition of claim 1, wherein the cellulose derivative (A) has a glass transition temperature Tg of 70 ° C or more and φ of less than 200 ° C. 4. The photocurable resin composition of claim 1 which contains a thermosetting component. 5. An alkali-developable photocurable resin composition comprising a cellulose derivative (A), a carboxyl group-containing resin (B), a photopolymerization initiator (C), and two or more molecules in a molecule The ethylenically unsaturated group compound (D). 6. The photocurable resin composition of claim 5, wherein φ wherein the cellulose derivative (A) is solvent-soluble. 7. The photocurable resin composition of claim 5, wherein the cellulose derivative (A) has a glass transition temperature Tg of 7 (TC or more, less than 200 ° C. 8. The photocurable resin composition of the fifth aspect, which contains the thermosetting component (E). 9. A photocurable dry film characterized by photocuring property according to any one of claims 1 to 8. The resin composition is coated on a carrier film and dried. -57-201007356. The hardened resin composition of any one of claims 1 to 8 or a photocurable resin composition thereof The composition is coated on a carrier film and obtained by photohardening a dried photocurable dry film. 11. A printed circuit board characterized by having the photohardening of any one of claims 1 to 8. The resin composition or a composition thereof is coated on a carrier film, and the photocured dry film obtained by drying is photohardened and then cured by heat curing. 12. The printed circuit of claim 1 Plate, wherein the aforementioned hardened film A printed circuit board characterized by having a hardened film containing a cellulose derivative (A). The printed circuit board according to claim 13, wherein the hardened film is a solder resist. 201007356 IV. Designation of representatives: (1) The designated representative circle of this case is: None. (2) Simple description of the symbol of the representative figure: None ❿ -3- 201007356 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: