TW201829614A - Photocurable resin composition, dry film, cured product, and printed circuit board - Google Patents

Abstract

Provided are: a photocurable resin composition capable of forming a cured product that has superior printing properties, i.e., free of oozing, streaks, etc., and superior crack resistance; a dry film having a resin layer obtained using the composition; a cured product obtained by curing the composition or the resin layer of the dry film; and a printed circuit board comprising the cured product. The photocurable resin composition contains (A) an epoxy (meth)acrylate having a urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C) a filler.

Description

Photocurable resin composition, dry film, cured product and printed wiring board

[0001] The present invention relates to a photocurable resin composition, a dry film, a cured product, and a printed wiring board.

[0002] In recent years, the requirements for miniaturization, high density, high definition, etc. of mobile phones, personal computers, touch monitors, etc. have increased day by day, and solder resists for printed wiring boards formed in these The fineness of insulating layers, conductive circuits, electrodes, etc., such as overlying layers or interlayer insulation, is also required to be larger than in the past. [0003] For these requirements, in order to apply the photolithography method which can be patterned more finely than the pattern printing method, an insulating paste or a conductive paste made of a photocurable resin composition is used to form an insulating layer or Conductive circuits, etc. (for example, refer to Patent Documents 1 to 6). [Prior Art Literature] [Patent Literature] [0004] Patent Literature 1: Japanese Patent Application Publication No. 2014-101412 Patent Literature 2: Japanese Patent Application Publication No. 2013-137511 Patent Literature 3: Japanese Patent Application Publication No. 2013-136727 4: International Publication No. 2010/113287 Patent Document 5: Japanese Patent Application Publication No. 2014-167090 Patent Document 6: Japanese Patent Application Publication No. 2015-026013

[Problems to be Solved by the Invention] [0005] Even if it is a photolithographic insulating paste or a conductive paste, in order to make only a small part removed by development, in fact, it is also used to print each paste pattern into a rough shape, followed by light micro Shadowing method to form high-definition patterns. Furthermore, a method of patterning a photocurable resin composition by pattern printing without using photolithography is also discussed. [0006] However, when the paste is pattern printed, if the actual paste pattern is too large than the pattern shape of the screen, defects such as poor installation during component mounting or short circuit caused by contact between conductors may occur. This means that the cream oozed out. An example of one reason for the oozing of the paste is the excessive amount of solvent in the paste. [0007] On the other hand, when the amount of solvent is reduced in order to suppress bleeding, the viscosity of the paste is too high, and the defect that the paste is not transferred to the substrate during pattern printing and the blank is broken, it is difficult to suppress both the bleeding and the break Line left blank. [0008] In addition, with the recent advances in the performance of electronic equipment, both insulating pastes and conductive pastes have become more important to the crack resistance of hardened products. As one of the methods for improving the crack resistance of the hardened material, a method of highly filled filler is exemplified. However, in the past, if the resin material is highly filled with fillers, the viscosity of the paste will increase significantly, and there is a problem of deterioration in printability. [0009] Therefore, an object of the present invention is to provide a photocurable resin composition capable of forming a cured product having excellent printability without bleeding or line blanking during pattern printing and having excellent crack resistance, A dry film of the resin layer obtained by the composition, its cured product, and a printed wiring board having the cured product. [Means to solve the problem] [0010] As a result of active research by the inventors, it was found that the epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol and the filler have excellent wettability And, if it is incorporated in a photo-curable resin composition, the viscosity of the paste can be reduced even without a large amount of solvent, and even high-fill fillers can maintain crack resistance and excellent printability, thus completing the present invention. [0011] That is, the photocurable resin composition of the present invention is characterized by containing (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, (B) photopolymerization Initiator and (C) filler. [0012] The photocurable resin composition of the present invention preferably the amount of the (C) filler is 70 to 95% by mass relative to the total mass of the photocurable resin composition. [0013] The photocurable resin composition of the present invention preferably has (A) the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group. [0014] The photocurable resin composition of the present invention preferably has the acid value of the (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton of 40 to 250 mgKOH / g Within. [0015] The photocurable resin composition of the present invention preferably has the glass transition temperature of the aforementioned (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton at -10 to 60 ° C Within. [0016] The dry film of the present invention is characterized by having a resin layer obtained by applying the photocurable resin composition to a film and drying it. [0017] The cured product of the present invention is characterized by curing the photocurable resin composition or the resin layer of the dry film. [0018] The printed wiring board of the present invention is characterized by having the aforementioned cured product. [Effects of the invention] According to the present invention, it is possible to provide a photocurable resin composition capable of forming a hardened product having excellent printability without bleeding or blanking during pattern printing, and having excellent crack resistance, A dry film having a resin layer obtained from the composition, a cured product thereof, and a printed wiring board having the cured product.

[0020] The photocurable resin composition of the present invention is characterized by containing (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, and (B) a photopolymerization initiator , And (C) filler. According to the results of active research by the present inventors, it has been found that by using an epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol, even if a large amount of a solvent is not used, it can become non-exudative And the viscosity of the paste such as broken wire and white. Furthermore, it can be seen that when the developability is imparted, when (A) the epoxy (meth) acrylate-based carboxyl group-containing resin having a urethane bond and a bisphenol AD skeleton is used, even if Na is used ₂ CO ₃ The development of a dilute alkali developer with a concentration of about 0.2% by mass can also suppress the occurrence of development residues and improve the resolution. This is because the urethane bond and the bisphenol AD skeleton show high wettability with the filler. And it is speculated that because of the development with a dilute alkaline aqueous solution, it is possible to form an image with less damage to the exposed portion. In addition, the resolution of the exposed area and the unexposed area to the alkaline developing solution is high, and the resolution is obtained. Improve. [0021] In addition, the photocurable resin composition of the present invention has excellent printability even with a high filler, and therefore, the filler can be contained in a high blending amount in order to increase crack resistance, conductivity, and the like. [0022] Furthermore, the photocurable resin composition of the present invention preferably contains a thermosetting component. In the past, for example, a conductive paste was fired at a high temperature to form a hardened material and adhered to the substrate, but in recent years, based on the viewpoint of the selectivity of the substrate, it has also been required to form the hardened material at a low temperature. When a thermosetting component is added to the photocurable resin composition of the present invention, a cured product excellent in adhesion can be formed even when cured at a low temperature. [0023] In this specification, the term (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions. [0024] The following describes each component that can be contained in the photocurable resin composition of the present invention that also contains optional components. [(A) Epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton] The photocurable resin composition of the present invention contains (A) having a urethane bond Epoxy (meth) acrylates that bind to the AD skeleton of bisphenol. (A) The epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton may also contain a carboxyl group. In this case, the photocurable resin composition of the present invention can be an alkali-developable type. In addition, when it does not have a carboxyl group, it can also become an alkali-developing type by blending with other alkali-soluble components. In addition, the bisphenol AD skeleton is also referred to as a bisphenol E skeleton in the technical field. [0026] (A) The synthesis method of the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is not particularly limited, but it can be, for example, added to a bisphenol AD epoxy resin The diol compound, and then the diisocyanate compound is slowly added, thereby obtaining the bisphenol AD epoxy urethane resin, which is further reacted with glycidyl (meth) acrylate to obtain a urethane bond And epoxy (meth) acrylate of bisphenol AD skeleton. In the present invention, as the component (A), it is preferable to use a structure obtained by reacting a bisphenol AD epoxy resin with a diol compound and further reacting with a diisocyanate compound as described above as a urethane bond and a bis Epoxy (meth) acrylate of phenol AD skeleton. [0027] In addition, (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group, that is, a bisphenol AD epoxy epoxy carbamate containing a carboxyl group The synthesis method for the (meth) acrylate resin is not particularly limited, but it can be obtained, for example, by reacting an epoxy (meth) acrylate having an urethane bond and a bisphenol AD skeleton with an acid anhydride. As mentioned above, the carboxyl group-containing resin has many free carboxyl groups on the side chain of the main polymer, so it can be developed by dilute alkaline aqueous solution. Moreover, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 250 mgKOH / g, more preferably in the range of 40 to 200 mgKOH / g, and still more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, it is preferable from the viewpoint of developability. On the other hand, if it is 250 mgKOH / g or less, from the viewpoint of dissolving the exposed portion with the developer to make the line thinner than necessary, it is preferable to prevent the deterioration of the dissolution contrast between the exposed portion and the unexposed portion. [0028] In addition, (A) the weight average molecular weight of the epoxy (meth) acrylate having an urethane bond and a bisphenol AD skeleton varies with the resin skeleton, but it is generally 2,000 to 150,000, and further For a range of 5,000 to 100,000. When the mass average molecular weight is 2,000 or more, it is preferable from the viewpoint of non-contact property, etc., and it is also preferable from the viewpoint of resolution in the case of alkali development type. On the other hand, when the mass average molecular weight is 150,000 or less, it is preferable from the viewpoint of storage stability and the like, and from the viewpoint of alkali developability, it is also preferable from the viewpoint of developability. The weight average molecular weight can be determined by gel permeation chromatography. [0029] (A) The glass transition temperature of the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is preferably in the range of -10 to 60 ° C. When the temperature is above -10 ℃, the non-touch performance is more excellent. At 60 ° C or lower, crack resistance is better. It is more preferably 0 to 40 ° C. [0030] The glass transition temperature of the (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton contained in the photocurable resin composition of the present invention can be determined by the photosensitive component The differential scanning calorimeter (DSC) is measured, and the examples in this specification are measured using this method. [0031] (A) An epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton can be used alone or in combination of two or more. [0032] The photocurable resin composition of the present invention may contain other photocurable resins within a range that does not hinder the curing of the present invention. [0033] [(B) Photopolymerization Initiator] (B) The photopolymerization initiator is not particularly limited, and for example, photopolymerization starting from oxime esters, acetophenones, benzophenones, and phosphine oxides can be used. Initial agent. In the present invention, (B) the photopolymerization initiator is preferably an oxime ester-based polymerization initiator having a group represented by the following general formula (I), or styrene having a group represented by the following general formula (II) Ketone photopolymerization initiator. [0034] [0035] In the general formula (I), R1 represents a hydrogen atom, an alkyl group having 1 to 6 carbons or a phenyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbons. In the general formula (II), R3 and R4 each independently represent an alkyl group having 1 to 12 carbons or an arylalkyl group having 6 to 12 carbons, and R5 and R6 each independently represent a hydrogen atom, or a carbon number 1 to 6 alkyl. Or R5 and R6 may be bonded together with the nitrogen atom in the formula to form a ring, and the ring may also contain an ether bond. As a specific example, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1 or 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. [0037] Among the aforementioned oxime ester-based photopolymerization initiators, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Corporation of Japan, N-1919, NCI-831 manufactured by ADEKA Corporation, and TOE- manufactured by Japan Chemical Industry Corporation 004, TR-PBG-304 made by Changzhou Qiangli Electronic New Materials Co., Ltd. is better. [0038] The foregoing acetophenone-based photopolymerization initiator having a group represented by the general formula (II) is exemplified by 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl Acetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Examples of commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 379EG manufactured by BASF Corporation of Japan. [0039] (B) The photopolymerization initiator may be used alone or in combination of two or more. [0040] (B) The blending amount of the photopolymerization initiator is not particularly limited, but it is 100 parts by mass relative to (A) epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol , Preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass. If it is 0.01 parts by mass or more, it is preferable from the viewpoint of photocurability, chemical resistance, and the like. On the other hand, if it is 30 parts by mass or less, it is preferable from the viewpoint of controlling the light absorption by the photopolymerization initiator on the surface of the cured coating film and improving the deep curability. [(C) Filler] The (C) filler is not particularly limited, and conventionally used inorganic or organic fillers can be used. The purpose of blending the (C) filler is not particularly limited, and may be to increase the physical strength of the coating film or to impart electrical conductivity. When imparting conductivity, a conductive filler is preferably used, and when the photocurable resin composition of the present invention is used to form an insulating layer, a non-conductive filler is preferably used. [0042] Any material can be used as long as the material of the conductive filler can impart conductivity to the photocurable resin composition of the present invention. Examples of such conductive fillers include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, etc., among these, preferred is Ag. These conductive fillers can be used in the form of the above-mentioned component monomers, or in the form of alloys or oxides. Furthermore, tin oxide (SnO ₂ ), Indium oxide (In ₂ O ₃ ), ITO (indium tin oxide), etc. In addition, the conductive filler may be carbon powder such as carbon black, graphite, carbon nanotube, and the like. However, it is necessary to pay attention because it reduces the light transmittance. [0043] The shape of the conductive filler is not particularly limited, and in addition to the flake shape, it is particularly preferably a needle shape or a spherical shape. Thereby, when the light transmittance is improved, or when the photocurable resin composition is an alkali development type, a conductive circuit or an electrode with excellent resolution can be formed. [0044] In order to form fine lines, the conductive filler preferably has a maximum particle diameter of 30 μm or less. By setting the maximum particle diameter to 30 μm or less, the photocurable resin composition can improve the resolution of a conductive circuit or an electrode when it is alkali-developed. [0045] In addition, as the conductive filler, an average particle diameter of 10 random random conductive fillers observed at 10,000 times using an electron microscope (SEM) is preferably in the range of 0.1 to 10 μm. When the average particle diameter is 0.1 μm or more, it is preferable from the viewpoint of conductivity. On the other hand, when the average particle diameter is 10 μm or less, it is preferable from the viewpoint of preventing clogging of the screen. In addition, those having an average particle diameter measured by MICROTACK of 0.5 to 3.5 μm are preferably used. The conductive filler is preferably 10 ^-3 Ω‧cm or less [0046] The non-conductive filler preferably has a volume inherent resistivity (JIS K 6911) of 10 ¹⁰ Non-conductive of Ω‧cm or more. Examples of non-conductive fillers include silica such as amorphous silica, fused silica, and spherical silica, barium sulfate, hydrotalcite, talc, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, and hydroxide. Aluminum, silicon nitride, aluminum nitride, boron nitride, Neuburger silica particles, etc. [0047] (C) The filler may be used alone or in combination of two or more. [0048] (C) The blending amount of the filler is based on the total mass of the photocurable resin composition, preferably 70 to 95 mass%, more preferably 70 to 90 mass%. If the blending amount of the filler is 70% by mass or more, it is preferable from the viewpoint of printability, and the viewpoint of conductivity when the conductive filler is blended is also preferable. On the other hand, if the blending amount of the filler is 95% by mass or less, it is preferable from the viewpoint of printability and light transmittance. [Reactive diluent] The photocurable resin composition of the present invention is preferably a reactive diluent for crosslinking with light. As the reactive diluent, (meth) acrylate compounds are preferably used. Furthermore, the reactive diluent is preferably polyfunctional. The reason why the polyfunctionality is better is that the photoreactivity is improved compared to when the number of functional groups is 1, and the resolution in the alkali-developing type is excellent. [0050] The (meth) acrylate compound is exemplified by a multifunctional (meth) acrylate monomer or oligomer (a (meth) acrylate monomer or oligomer having 2 or more functions), and specific examples are, for example, Commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate Wait. Specific examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylic esters; Acrylic amides such as N, N-dimethylacrylamide, N-hydroxymethylacrylamide, N, N-dimethylaminopropylpropylacrylamide; Acrylic N, N- Aminoalkyl acrylates such as dimethylaminoethyl ester, N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, ginsyl-hydroxyethyl isocyanide Polyacrylates such as urea ester polyols or such ethylene oxide adducts, propylene oxide adducts, or epsilon-caprolactone adducts; phenoxy acrylates, bisphenol A Diacrylates and polyacrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylol Polyacrylic esters of glycidyl ethers such as propane triglycidyl ether, triglycidyl isocyanurate, etc .; not limited to the above, but also polyethers Polyols such as monohydric alcohols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, etc. are directly acrylated, or acrylates and melamine acrylates which are acrylated with urethane through diisocyanate , And at least any one of the methacrylates corresponding to the above acrylate. [0051] Furthermore, an epoxy acrylate resin obtained by reacting a multifunctional epoxy resin such as a cresol novolac epoxy resin with acrylic acid, or further a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate, etc. Epoxy urethane acrylate compounds obtained by reacting hydroxy acrylates with isophorone diisocyanate and other diisocyanate semi-urethane compounds can also be used as reactive diluents. These epoxy acrylate resins can reduce the dryness of the touch and improve the photocurability. Among them, polyfunctional (meth) acrylate monomers are preferably used, and tetrafunctional (meth) acrylate monomers are particularly preferred. Examples of 4-functional (meth) acrylate monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and the like. [0053] The reactive diluent may be used alone or in combination of two or more. [0054] The blending amount of the reactive diluent is not particularly limited, and it is preferably 10 to 100 parts by mass of the epoxy (meth) acrylate having (A) an urethane bond and an bisphenol AD skeleton. 100 parts by mass, preferably 20 to 80 parts by mass. When it is 10 parts by mass or more, the photocurability is good, and it is easy to form a pattern line in alkali development after irradiation with active energy rays. On the other hand, when it is 100 parts by mass or less, the solubility in the alkaline aqueous solution is good, and the patterned film is less likely to become brittle. [0055] (Thermosetting component) The photocurable resin composition of the present invention preferably contains a thermosetting component in order to further improve crack resistance. As the thermosetting component used in the present invention, amine resins such as melamine resins, benzoguanamine resins, blocked isocyanate compounds, cyclic carbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, Thermosetting resins such as episulfide resins, melamine derivatives, etc. A thermosetting component can be used individually by 1 type or in combination of 2 or more types. In the present invention, it is preferably a thermosetting component selected from at least one of two or more cyclic ether groups and cyclic thioether groups in the molecule (hereinafter referred to as cyclic (thio) ether group), or 1 molecule Thermosetting component with two or more isocyanate groups or blocked isocyanate groups. [0056] The thermosetting component having two or more cyclic (thio) ether groups in the above molecule is any cyclic ether group or cyclic thioether group having two or more 3, 4 or 5 member rings in the molecule One or two kinds of compounds can be exemplified by, for example, compounds having at least two epoxy groups in the molecule, that is, polyfunctional epoxy compounds, compounds having at least two oxetanyl groups in the molecule, or That is, a multifunctional oxetane compound, a compound having more than two thioether groups in the molecule, that is, an episulfide resin, etc. Examples of the aforementioned multifunctional epoxy compound include, for example, JER828, JER834, JER1001, JER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055 manufactured by DIC Corporation, and EPOTOT YD manufactured by Toto Chemical Co., Ltd. -011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA manufactured by Sumitomo Chemical Industries -128, AER330, AER331, AER661, AER664 and other bisphenol A type epoxy resins manufactured by Asahi Kasei Chemicals Corporation; JERYL 903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 and Epiclon 165 manufactured by DIC Corporation, and EPOTOT YDB manufactured by Toto Chemical Industries -400, YDB-500, DER542 manufactured by Dow Chemical Company, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, and brominated epoxy resins such as AER711 and AER714 manufactured by Asahi Kasei Chemicals; Mitsubishi Chemical Corporation Manufactured by JER 152, JER 154, DEN431 and DEN438 by Dow Chemical Company, Epiclon N-730, Epiclon N-770, Epiclon N-865 by DIC, and EPOTOT YDCN-701 and YDCN-704 by Toto Chemical Co., Ltd. Nippon Kayaku Of EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, and AER ECN-235, ECN- manufactured by Asahi Kasei Corporation Novolac epoxy resins such as 299; Epiclon 830 manufactured by DIC Corporation, JER 807 manufactured by Mitsubishi Chemical Corporation, and EPOTOT YDF-170, YDF-175, YDF-2004 and other bisphenol F epoxy resins manufactured by Toto Chemical Co., Ltd. Resin; EPOTOT ST-2004, ST-2007, ST-3000, etc. hydrogenated bisphenol A epoxy resin manufactured by Toto Chemical Co., Ltd .; JER 604 manufactured by Mitsubishi Chemical Corporation, EPOTOT YH-434 manufactured by Toto Chemical Co., Ltd .; Sumitomo Chemical Sumi-epoxy ELM-120 and other glycidyl amine epoxy resin; Hydantoin type epoxy resin; Celloxide 2021P and other alicyclic epoxy resins manufactured by Dicel; Mitsubishi Chemical Corporation YL -933, trihydroxyphenylmethane type epoxy resins such as TEN, EPPN-501, EPPN-502, etc. manufactured by Dow Chemical Company; bis-dimethyl YL-6056, YX-4000, YL-6121, etc. manufactured by Mitsubishi Chemical Corporation Phenol-type or biphenol-type epoxy resin or a mixture of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd. EPX-30, EXA-1514 and other bisphenol S type epoxy resin manufactured by DIC; JER 157S and other bisphenol A novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation; JERYL-931 manufactured by Mitsubishi Chemical Corporation Tetrahydroxyphenylethane type epoxy resin; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industry Co .; diglycidyl phthalate resin such as Blenmer DGT manufactured by Nippon Oil & Fats Company; Four glycidyl xylyl ethane resins such as ZX-1063 made by Chemical Industry Co., Ltd .; ESN-190, ESN-360 made by Nippon Steel Chemical Co., and HP-4032, EXA-4750, EXA- made by DIC Epoxy resin containing naphthyl group such as 4700; epoxy resin with dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; CP-50S and CP-50M manufactured by Japan Oil and Fats Corporation Glycidyl methacrylate copolymer-based epoxy resin; furthermore, copolymerized epoxy resin with cyclohexyl maleimide and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (For example, EPOLEAD PB-3600 manufactured by Daicel, etc.), CTBN modified epoxy resin (for example, Dongdu Chemical Co., Ltd. The system YR-102, YR-450, etc.) and the like, but is not limited to such. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins, or mixtures of these are particularly preferred. [0058] The foregoing multifunctional oxetane compound is exemplified by bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethyl Oxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxa (Cyclobutylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, methacrylic acid ( Multifunctional oxa such as 3-methyl-3-oxetanyl) methyl ester, (3-ethyl-3-oxetanyl) methyl methacrylate or such oligomers or copolymers Cyclobutanes, as well as oxetane alcohol and novolak resins, poly (p-hydroxystyrene), cardo bisphenols, calixarenes, calixarene aromatics (calixresorcinarene), or ether compounds such as silsesquioxane and resins with hydroxyl groups. In addition, copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates, etc. are also cited. Examples of the compound having two or more cyclic sulfide groups in the aforementioned molecule are, for example, bisphenol A-type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. In addition, an epoxy resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is replaced with a sulfur atom by the same synthesis method can also be used. [0060] Furthermore, in the photocurable resin composition of the present invention, in order to improve the curability of the photocurable resin composition and the strength and toughness of the resulting cured film, it is preferable to add two or more isocyanate groups or sealers in one molecule. Compounds with terminal isocyanate groups. Examples of such compounds having 2 or more isocyanate groups or blocked isocyanate groups in 1 molecule are compounds having 2 or more isocyanate groups in 1 molecule, that is, polyisocyanate compounds, or compounds having 2 or more in 1 molecule Compounds that block isocyanate groups, that is, blocked isocyanate compounds, etc. [0061] As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and o- Xylene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of aliphatic polyisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl Isocyanate) and isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is bicycloheptane triisocyanate. As well as the adducts of isocyanate compounds previously listed, the urea body and the isocyanurate body, etc. [0062] The blocked isocyanate group contained in the blocked isocyanate compound is a temporarily inertized group protected by reacting the isocyanate group with the blocking agent. When heated to a specific temperature, the blocking agent dissociates to form isocyanate groups. [0063] As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As the isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate as described above is used. [0064] The isocyanate blocking agent can be exemplified by phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; ε-caprolactam, δ-valerolactam, γ-butane Endoamide-based end-capping agents such as internal amide and β-propionylamide; active methylene-based end-capping agents such as ethyl acetate and ethyl acetone; 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, benzyl ether, glycolic acid methyl ester Alcohol end-capping agents such as esters, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketoxime, diethyl acetyl oxime , Cyclohexane oxime and other oxime-based capping agents; butyl mercaptan, hexyl mercaptan, third butyl mercaptan, thiophenol, methylthiophenol, ethylthiophenol and other mercaptan-based capping agents; Acetamide-based blocking agents such as amide and benzamide; amide-based blocking agents such as succinate and imidate maleate; dimethylaniline, aniline, butylamine, Amine blocking agents such as dibutylamine; imidazole, Imidazole-based blocking agents such as 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propylimine. [0065] The blocked isocyanate compound may also be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7901, 7992 (above manufactured by Baxenden), Smidur BL-3175, BL-4165, BL -1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosome 2170, Desmosome 2265 (above manufactured by Sumitomo Bayer Carbamate), Coronate 2512, Coronate 2513, Coronate 2520 (above manufactured by Japan Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd.), DURANATE TPA- B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Corporation), KARENZ MOI-BM (manufactured by Showa Denko Corporation), etc. In addition, Sumidur BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a blocking agent. [0066] 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. [0067] The compounding amount of the compound having 2 or more isocyanate groups or blocked isocyanate groups in 1 molecule is relative to (A) an epoxy (meth) group having a urethane bond and a bisphenol AD skeleton ) 100 parts by mass of acrylate, preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass. When it is 1 part by mass or more, it is preferable from the viewpoint of the toughness of the coating film. On the other hand, when it is 100 parts by mass or less, it is preferable from the viewpoint of storage stability. [0067] The photocurable resin composition of the present invention may contain the other components exemplified below in order to further enhance the fat effect of the present invention or to further exert other effects in a range that does not hinder the effect of the present invention. (Organic acid) The organic acid is preferably an organic acid having no aromatic ring. By matching with an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself can be suppressed and the (A) epoxy (meth) acrylate with a carbamate bond and an AD skeleton of bisphenol can be relatively improved Light reactivity, excellent resolution can be obtained. Among them, dicarboxylic acid is preferred, and 2,2'-thiodiacetic acid is more preferred. [0070] Specific examples of organic acids are 2,2'-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, propanediol Acids, butyric acid, malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid and other carboxylic acids; dibutyl phosphite, butyl phosphite, dimethyl phosphite Ester, methyl phosphite, dipropyl phosphite, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, n-methyl-2-phosphite Mono- or diesters of phosphorous acid such as ethylhexyl ester; dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, Mono- or diesters of phosphoric acid such as diisopropyl phosphate, isopropyl phosphate, n-butyl-2-ethylhexyl phosphate, etc. [0071] The blending amount of the organic acid is preferably 1 to 10 parts by mass relative to 100 parts by mass of the (A) epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol. Scope. When it is 1 part by mass or more, the developability is better, and on the other hand, when it is 10 parts by mass or less, the resolution is more excellent. [0072] (Dispersant) By blending the dispersant, the dispersibility and settling properties of the photocurable resin composition can be improved. [0073] Examples of the dispersant are, for example, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK -108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163 , DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK -191, DISPERBYK-192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-2150, BYK-P104 , BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (made by Japan BYK), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DI SPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50 (manufactured by Nanben Chemical Industry Co., Ltd.), FLOREN G-450, FLOREN G-600, FLOREN G-820, FLOREN G-700, FLOREN DOPA-44, FLOREN DOPA -17 (produced by Kyoeisha Chemical Company). [0074] In order to effectively achieve the above purpose, the content of the dispersant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the filler. [0075] (Photopolymerization Inhibitor) By adding a photopolymerization inhibitor, a certain amount can be suppressed according to the type and addition amount of the polymerization inhibitor within the radical polymerization inside the photocurable resin composition by exposure Radical polymerization. This can suppress the light response to weaker light such as scattered light. Therefore, a finer conductive circuit line can be clearly formed, so it can be used better. The photopolymerization inhibitor is not particularly limited as long as it can be used as a photopolymerization inhibitor, and examples thereof include, for example, p-benzoquinone, naphthoquinone, di-tert-butyl‧p-cresol, hydroquinone monomethyl ether, and α-naphthol , Acetamidine acetate, hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid, quinodioxime, pyrogallol, tannic acid (tannic acid), resorcinol, N-hydroxy N-nitroso-aniline ammonium salt (Cupferron), phenothiazine (phenothiazine), etc. [0076] (Thermosetting Catalyst) When the thermosetting component having two or more cyclic (thio) ether groups in the molecule is used in the photocurable resin composition of the present invention, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts are imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives such as ethyl ethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4 -(Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzyl Amine compounds such as amines, adipic hydrazide compounds such as adipic acid dihydrazide, sebacic acid dihydrazine, and phosphorus compounds such as triphenylphosphine. In addition, the marketers include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT3503N, U manufactured by SAN-APRO -CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. It is not particularly limited to these, preferably a thermosetting catalyst of epoxy resin or oxetane compound, or to promote the reaction of at least any one selected from epoxy group and oxetanyl group with carboxyl group, ie Yes, it does not matter if one kind is used alone or two or more kinds are mixed. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine‧isocyanuric acid adduct, 2,4-diamino-6-methacrylic S-triazine derivatives such as acetoxyethyl-S-triazine‧isocyanuric acid adducts are preferably used in combination with the aforementioned thermosetting catalyst and also function as these adhesion imparting agents. [0077] The mixing amount of the thermosetting catalysts is sufficient in a normal ratio, for example, with respect to 100 masses of thermosetting components having two or more cyclic (thio) ether groups in a carboxyl group-containing resin or molecule Parts, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass. [0078] (Thermal Polymerization Inhibitor) The thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the photocurable resin composition of the present invention. Examples of thermal polymerization inhibitors are, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, third butyl catechol, pyrogallol, 2-hydroxybenzophenone, 4 -Methoxy-2-hydroxybenzophenone, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2 , 2'-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper react with organic chelating agent Compounds, methyl salicylate, nitroso compounds, chelate compounds of nitroso compounds and Al, etc. (Chain transfer agent) In the photocurable resin composition of the present invention, in order to improve sensitivity, N-phenylglycine acids, phenoxyacetic acids, and thiophenoxy groups known as chain transfer agents can be used. Acetic acid, mercaptothiazole, etc. If a specific example of a chain transfer agent is given, it is, for example, a chain transfer agent having a carboxyl group such as mercaptosuccinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzene mercaptan and derivatives thereof, chain transfer agents with hydroxyl groups; 1-butanethiol, butyl-3-mercaptopropionic acid Ester, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan, propane Mercaptan, butane mercaptan, pentane mercaptan, 1-octane mercaptan, cyclopentane mercaptan, cyclohexane mercaptan, thioglycerol, 4,4-thiodiphenyl mercaptan, etc. [0080] Furthermore, a multifunctional thiol-based compound can be used without particular limitation, but for example, hexane-1,6-dithiol, decane-1,10-dithiol, and dimercaptodiethyl ether can be used. , Aliphatic thiols such as dimercaptodiethyl sulfide, aromatic thiols such as xylene dithiol, 4,4'-dimercaptodiphenyl sulfide, 1,4-benzenedithiol; B Glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerol ginseng (mercaptoacetate), trimethylolethane ginseng ( (Mercaptoacetate), trimethylolpropane ginseng (mercaptoacetate), pentaerythritol (mercaptoacetate), dipentaerythritol (mercaptoacetate) and other polyalcohols (mercaptoacetate); Ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerol ginseng (3-mercaptopropionate) , Trimethylolethane ginseng (mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol (3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate) Propionate) Poly (3-mercaptopropionate) s such as polyols; 1,4-bis (3-mercaptobutyryloxy) butane , 1,3,5-ginseng (3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, pentaerythritol (3- Mercaptobutyrate) and other poly (mercaptobutyrate). Examples of such commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (above manufactured by Sakai Chemical Industry Co., Ltd.), KARENZ MT-PEI, KARENZ MT-BDI and KARENZ-NR1 (above manufactured by Showa Denko) and others. [0082] Furthermore, examples of the heterocyclic compound having a mercapto group functioning as a chain transfer agent are, for example, mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto -4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-thiobutyrolactone (butyrothiolactone), 2-mercapto-4-butyrolactone Acetamide, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butane Acetamide, N-ethyl-2-mercapto-4-butyralamide, N- (2-methoxy) ethyl-2-mercapto-4-butyrolamide, N- (2-ethoxy ) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-pentanolactam Amine, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) Ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4, 6-trimercapto-s-triazine (ZISNET F manufactured by Sankyo Chemical Co., Ltd.), 2-dibutylamino-4,6-dimercapto-s-triazine (ZISNET DB manufactured by Sankyo Chemical Co., Ltd.), and 2- Anilino-4,6-dimercapto-s-tri (Sankyo Kasei Co., Ltd. ZISNET AF) and the like. [0083] In particular, a heterocyclic compound having a mercapto group as a chain transfer agent that does not impair the visibility of the photocurable resin composition is preferably 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2 -Mercaptobenzothiazole (AXEL M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole- 2-mercaptan, 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents can be used alone or in combination of two or more. [Other added components] Of course, the photo-curable resin composition of the present invention can also be appropriately matched with conventional and conventional components as needed, such as tackifiers, defoaming and leveling agents, coupling agents, antioxidants, and rust inhibitors. Agents, colorants, organic solvents, etc. [0085] The photocurable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-liquid or more than two-liquid. When the film is dried, the photocurable resin composition of the present invention is applied to the film and dried to form the resulting resin layer. After the resin layer is formed, for the purpose of preventing dust and the like from adhering to the film surface, it is preferable to further laminate a peelable film on the film surface. [Formation of Photohardenable Coating Film] (A) When the epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol has a carboxyl group, it can be patterned by photolithography . Hereinafter, an example of a method of forming a photo-curable coating film by photolithography using the photo-curable resin composition of the present invention will be described. [0087] In the photocurable resin composition of the present invention, a kneading and dispersion of the above-mentioned essential components and optional components uses a machine such as a three-roller or a blender. The photo-curable resin composition thus dispersed is applied onto the substrate by a suitable coating method such as screen printing method, bar coater, blade coater and the like. [0088] After coating, the coating film is dried in order to obtain dryness to the touch. The drying method is not particularly limited. For example, a hot-air circulation drying furnace, a far-infrared drying furnace, etc. are used to prevent (A) the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton from thermally decomposing, for example, about 60 ~ Dry at 120 ℃ for 5 ~ 40 minutes to evaporate the organic solvent to obtain a non-tacky coating film. [0089] Next, contact exposure or non-contact exposure is performed using a negative mask having a specific exposure pattern. As the exposure light source system, halogen lamps, high-pressure mercury lamps, laser light, metal halide lamps, black lamps, electrodeless lamps, etc. are used. As for the exposure, the cumulative light can be 200mJ / cm ² The following low light levels. In addition, it is also possible to use a laser direct imaging device to form a pattern on the coating film without using a mask. [0090] Next, the coating film is patterned by development by spraying method, dipping method, or the like. As the developer, an alkaline aqueous solution of metal such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, or an aqueous solution of amine such as monoethanolamine, diethanolamine, and triethanolamine is preferably used. In particular, a dilute alkaline aqueous solution having a concentration of about 1.5% by mass or less can be preferably used, but as long as the carboxyl group in the photocurable resin composition is saponified to remove the uncured part (unexposed part), it is not limited to Developer. [0091] According to the photocurable resin composition of the present invention, by using a dilute alkaline aqueous solution as a developing solution, the damage to the coating film is small, and the problem of developing residue is not generated, and a photocurable coating with excellent resolution is obtained. membrane. [0092] Therefore, in one aspect of the present invention, the developer used in the method of forming the photocurable coating film is preferably Na ₂ CO ₃ Dilute alkaline aqueous solution with a concentration of 0.1 to 2.0% by mass, preferably Na ₂ CO ₃ Dilute alkaline aqueous solution with a concentration of 0.2 ~ 1.0% by mass. [0093] After development, in order to remove unnecessary developer after development, it is preferable to perform water washing or acid neutralization. [0094] Next, the resulting photocurable coating film is cured at a temperature that does not thermally decompose (A) the epoxy (meth) acrylate having the urethane bond and the bisphenol AD skeleton. This can form a cured coating film excellent in printability and excellent in adhesion and crack resistance. The thermal hardening temperature is preferably 180 ° C or lower, more preferably 150 ° C or lower, still more preferably 140 ° C or lower, and particularly preferably 130 ° C or lower. [0095] In these steps, a resin-made substrate that does not have heat resistance can be used as the substrate. Specifically, examples of the resin-made substrate include polyimide, polyester resin, polyether sock (PES), polystyrene (PS), polymethyl methacrylate (PMMA), and polycarbonate. (PC), polyamide (PA), polypropylene (PP), polyphenylene ether (PPO), etc., and polyester resins can be preferably used. Also, it may be a glass substrate or the like. In addition, as the above-mentioned base material, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed by copper or the like in advance, examples of the use of paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyamide Copper layer for high-frequency circuits such as imine, glass cloth / nonwoven epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluororesin, polyethylene, polyphenylene oxide, polyphenyl oxide, isocyanate, etc. Plywood and other materials, and examples are all grades (FR-4, etc.) copper-clad laminates, in addition to glass substrates, metal substrates, polyimide film, PET film, polyethylene naphthalate (PEN) Thin films, ceramic substrates, wafer boards, etc. [0096] The photocurable resin composition of the present invention can be preferably used for conductive circuits, electrodes, electromagnetic wave shielding formation, conductive adhesives, etc. It is also preferably used for forming a cured film on a printed wiring board In other words, as a printed wiring board, it is more preferably used to form a permanent coating, and further preferably used to form a solder resist or a protective layer or an interlayer insulating material. Tejia is used to form a flux resist, that is, as a flux resist composition. In addition, the photocurable resin composition of the present invention can also be used to form a flux dam. [Examples] [0097] The present invention will be specifically described below based on examples. However, the present invention is not limited to these embodiments. [Synthesis of Epoxy Acrylate (A-1) with Carbamate Bonding and Bisphenol AD Framework> Bisphenol AD Epoxy Resin R-710 (Mitsui Chemical Co., Ltd.): 174g ( 0.5mol) was dissolved in carbitol acetate: 500mL, 2-methylhydroquinone: 0.5g and 1,6-hexanediol as a diol compound: 142g (1.2mol) were added to the solution, and the temperature was raised To 45 ° C. To this solution was added hexamethylene diisocyanate as a diisocyanate compound: 202 g (1.2 mol), and the solution was slowly added dropwise so that the reaction temperature did not exceed 50 ° C. After the dropwise addition, the temperature was raised to 80 ° C, and the reaction was carried out for 6 hours until 2250 cm by infrared absorption spectrometry ^-1 Until the nearby absorption disappears. After adding 171 g (1.2 mol) of glycidyl methacrylate as an epoxy compound having an unsaturated double bond in the molecule to this solution, the temperature was raised to 95 ° C. and the reaction was carried out for 6 hours to obtain a carbamate bond. And bisphenol AD skeleton epoxy acrylate (A-1) resin solution. The solid content is 55% by mass, and the Tg measured by DSC is 25.3 ° C. [Synthesis of Epoxy Acrylate (A-2) with Carbamate Bonding and Bisphenol AD Framework> In addition to using isophorone diisocyanate: 267 g (1.2 mol) as the isocyanate compound, and ( The method of A-2) reacts under the same conditions to obtain a resin solution of an epoxy acrylate (A-2) having a urethane bond and an AD skeleton of bisphenol. The solid content is 50% by mass, and the Tg measured by DSC is 26.5 ° C. [Synthesis of epoxy acrylate (A-3) having a carboxyl group, having a urethane bond and a bisphenol AD skeleton> As a ring having a urethane bond and a bisphenol AD skeleton A 53% by weight solution of oxyacrylate (A-1): 433 g, fed with triphenylphosphine: 0.5 g and tetrahydrophthalic anhydride: 183 g (1.2 mol), and reacted at 110 ° C. for 5 hours with stirring. As a result, a resin solution of an epoxy acrylate (A-3) having a carboxyl group and having a urethane bond and a bisphenol AD skeleton is obtained. The solid content is 51% by mass, the solid content acid value is 85 mgKOH / g, and the Tg measured by DSC is 19.2 ° C. [Synthesis of epoxy acrylate (A-4) having a carboxyl group, having a urethane bond and a bisphenol AD skeleton> Except for using a ring having a urethane bond and a bisphenol AD skeleton 50% by weight solution of (A-2) of oxyacrylic acid ester: except 476g, the reaction was carried out under the same conditions as the method of (A-3) to obtain a carboxyl group, a carbamate bond and a bisphenol AD skeleton Resin solution of epoxy acrylate (A-4). The solid content is 53% by mass, the solid content acid value is 82 mgKOH / g, and the Tg measured by DSC is 21.3 ° C. [0102] Here, the acid value means a value measured by the following method according to the method described in "JIS K 2501-2003 Petroleum Products and Lubricating Oils-Neutralization Test Method". And the acid value described later is the same. [Measurement method of acid value] The sample was dissolved in a titration solvent in which xylene and dimethylformamide were mixed at a mass ratio of 1: 1, and 0.1 mol / L potassium hydroxide was used by potentiometric titration Titration of ethanol solution. Taking the turning point on the titration curve as the end point, the acid value is calculated from the titration amount from the potassium hydroxide solution to the end point. [Preparation of Photocurable Resin Composition] The components of the agent contained in the following Tables 1 and 2 are blended and stirred, and dispersed three times using a three-roll kneading machine. Subsequently, carbitol acetate was added as a solvent to make the paste viscosity 250 dPa‧s ± 20 Pa‧s to obtain each photocurable resin composition described in the table. [0105] <Evaluation Method> [0106] (Viscosity) Each photo-curable resin composition prepared according to the above [Preparation of Photo-curable Resin Composition] uses a cone-plate type viscometer TVE-33H manufactured by Toki Industries Co., Ltd. The shape of the body rotor was 3 ° R9.7, and the viscosity was measured at 25 ° C and the rotation speed of the cone rotor 5 rpm. [Method for producing test piece for evaluation of bleed out and blanking of breakage] The photocurable resin composition described in Tables 1 and 2 below is washed with a frosted roller and dried, and then a glass with a thickness of 1.6 mmt On the epoxy resin substrate, a SUS calender made of 380 mesh, 100μm / 100μm line and space (L / S) was used, and the pattern coating was performed so that the film thickness after drying became 5μm, followed by hot air circulation The drying oven was dried at 80 ° C for 30 minutes to prepare test pieces with good finger drying. (Bleeding) The test piece prepared by the above method was observed using an optical microscope, and the bleeding amount was calculated from the following formula (1) and evaluated. Exudation amount (μm) = actual pattern width (μm)-100 μm ... Formula (1) [0109] (Broken line blank) Visually observe the test piece produced by the above method, and evaluate the degree of broken line blanking of the dried coating film. ○: There is no breakage on the dry coating film. △: There was a little breakage and blanking on the dried coating film. ×: The dry coating film clearly has broken lines and white space. [0110] (Preparation of Test Piece for Evaluation of Adhesion and Crack Resistance) The photocurable resin composition described in Tables 1 and 2 below was washed with a frosted roller and dried to a plate thickness of 1.6 mmt On the glass epoxy resin substrate, use 380 mesh, 100μm / 100μm line and space (L / S) SUS calendering plate, coated in such a way that the film thickness after drying becomes 5μm, followed by hot air circulation Type drying oven at 80 ℃ for 30 minutes to form a coating film with good finger touch drying. Subsequently, a high-pressure mercury lamp was used as a light source so that the accumulated light amount on each photocurable resin composition became 500 mJ / cm ² Full exposure. Finally, it was cured at 150 ° C for 60 minutes to prepare a test piece for evaluation of crack resistance. (Adhesiveness) For the line / space (L / S) of L / S = 100 μm / 100 μm produced by the above method, glass tape (registered trademark) was peeled off to evaluate the adhesiveness. ○: The thread is completely free of defects. △: There are quite few wire defects. ×: There is a large line defect. (Crack resistance) A bending operation in which the test piece produced by the above method was alternately bent and restored with the pattern as the inside and outside was performed, and the presence or absence of cracks was observed with an optical microscope and evaluated. ◎: The bending action was repeated more than 30 times without cracking. ○: The bending action was repeated more than 20 times and had cracks less than 30 times. △: The bending action was repeated 10 times or more and cracked after less than 20 times. ×: The bending action was repeated for less than 10 times with cracks. [0113] (Method for producing test piece for evaluation of resolution) The photocurable resin composition described in Tables 1 and 2 below is blended with a carboxyl group-containing epoxy acrylate photocurable resin composition, After grinding with a frosting roller, the glass epoxy substrate with a thickness of 1.6mmt is washed and dried, and then a 380 mesh SUS calender plate is used. The dried film thickness is 5μm, and then coated with hot air The circulating drying oven was dried at 80 ° C for 30 minutes to produce a coating film with good finger drying. Subsequently, a high-pressure mercury lamp was used as a light source, and a negative mask with a line of 30 μm / 40 μm and a gap (L / S) was interposed so that the cumulative light amount on each photocurable resin composition became 500 mJ / cm ² Pattern exposure. Then use Na at 30 ℃ ₂ CO ₃ A 0.2% by mass sodium carbonate aqueous solution was developed and washed with water. Finally, it was cured at 150 ° C for 60 minutes to prepare a test piece for evaluation of resolution. [Resolvability] The resolution of 30 μm / 40 μm line and space (L / S) of the test piece was evaluated. ○: The thread is completely free of defects. △: The thread is slightly defective. ×: There is a substantial defect in the thread. [0115] The test results are summarized in Tables 1 and 2. In addition, the numerical values related to each component in Tables 1 and 2 without units are indicated as mass parts. [0116] [0117] * 1: A-1, epoxy (meth) acrylate with urethane bond and bisphenol AD skeleton, solid content 55% by mass, the blending amount in the table is the blending amount of resin solution * 2: A-2, epoxy (meth) acrylate with urethane bond and bisphenol AD skeleton, solid content 50% by mass, the blending amount in the table is the blending amount of resin solution * 3: A-3 , Epoxy (meth) acrylate with carboxyl group, carbamate linkage and bisphenol AD skeleton, solid content 51% by mass, solid content acid value 85 mgKOH / g, the blending amount in the table is resin solution Mixing amount * 4: A-4, epoxy (meth) acrylate with carboxyl group, urethane bond and bisphenol AD skeleton, solid content 53% by mass, solid content acid value 82 mgKOH / g , The blending amount in the table is the blending amount of the resin solution * 5: KAYARAD UXE-3000, a carboxyl group-containing bisphenol A type carbamate epoxy acrylate made by Nippon Kayaku Co., solid content 65% by mass, solid form The acid value is 100 mgKOH / g, and the blending amount in the table is the blending amount of the resin solution * 6: KAYARAD ZFR-1401H, a bisphenol A type carbamate epoxy acrylate containing carboxyl group manufactured by Nippon Kayaku Co., Ltd., Solid content 63% by mass, solid content acid value 100 mgKOH / g, the blending amount in the table is the blending amount of the resin solution * 7: filler, BARIACE B-30 manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate * 8: filler, Ronson FUSELEX WX manufactured by the company, silica * 9: filler, A-50-K manufactured by Showa Denko Corporation, alumina * 10: filler, TIPAQUE CR-97 manufactured by Ishihara Industries, titanium oxide * 11: filler, AG3 manufactured by DOWA Electronics -8F, silver powder * 12: photopolymerization initiator, IRGACURE OXE02 made by BASF Japan * 13: photopolymerization initiator, IRGACURE 907 made by BASF Japan * 14: reactive diluent, NK OLIGO by Shin Nakamura Chemical Industry Co., Ltd. U-4HA, 4-functional urethane acrylate * 15: reactive diluent, KAYARAD TMPTA manufactured by Nippon Chemical Co., trimethylolpropane triacrylate * 16: reactive diluent, NK manufactured by Shin Nakamura Chemical Co., Ltd. ESTER A-TMMT, pentaerythritol tetraacrylate * 17: reactive diluent, KAYARAD DPHA manufactured by Nippon Chemical Co., dipentaerythritol hexaacrylate * 18: thermosetting component, JER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin * 19: Thermosetting component, DURANATE MF-B60B manufactured by Asahi Kasei Corporation, blocked isocyanate * 20: Dispersant, DISPERBYK-191 manufactured by BYK Corporation, Japan * 21: Organic acid, manufactured by Kanto Chemical Co., 2,2'-thio Diacetic acid * 22: Solvent, IPSOL 150 manufactured by Idemitsu Kosei Corporation, petroleum-based solvent [0118] From the results shown in the above table, it can be seen that the photocurable resin composition of the present invention can form a cured product having excellent printability without bleeding or blanking, etc., and having excellent crack resistance.

Claims (8)

A photocurable resin composition characterized by containing (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C )filler. The photocurable resin composition according to claim 1, wherein the blending amount of the aforementioned (C) filler is 70 to 95% by mass relative to the total mass of the photocurable resin composition. The photocurable resin composition according to claim 1, wherein the (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group. The photocurable resin composition according to claim 3, wherein the (A) epoxy (meth) acrylate having an urethane bond and an AD skeleton of bisphenol has an acid value of 40 to 250 mgKOH / g Within. The photocurable resin composition according to claim 1, wherein the glass transition temperature of the (A) epoxy (meth) acrylate having a urethane bond and an AD skeleton of bisphenol is -10 to 60 ° C Within. A dry film characterized by having a resin layer obtained by applying the photocurable resin composition of claim 1 to a film and drying it. A cured product characterized by hardening the photocurable resin composition of any one of claims 1 to 5 or the resin layer of the dry film of claim 6. A printed wiring board characterized by having the hardened product of claim 7.