JP2018053189A - Photocurable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of forming a cured product which has excellent printability without exudation or fading and has excellent crack resistance; a dry film having a resin layer obtained from the composition; and a cured product obtained by curing a resin layer of the composition or the dry film and a printed wiring board having the cured product.SOLUTION: A photocurable resin composition contains (A) epoxy (meth)acrylate having an urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C) a filler.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable insulating composition, a dry film, a cured product, and a printed wiring board.

  In recent years, there has been an increasing demand for miniaturization, high density, high definition, etc. in mobile phones, personal computers, touch panel displays, etc., and insulation such as solder resist, coverlay and interlayer insulation of printed wiring boards formed on these. Refinement of layers, conductive circuits, electrodes, and the like has been increasingly demanded.

  In response to such demands, in order to apply a photolithography method capable of high-definition patterning compared to the pattern printing method, an insulating layer or a conductive circuit using an insulating paste or conductive paste made of a photocurable resin composition is used. Etc. (see, for example, Patent Documents 1 to 6).

JP 2014-101212 A JP2013-137511A JP 2013-136727 A International Publication No. 2010/113287 JP 2014-167090 A Japanese Patent Laying-Open No. 2015-026013

  Even if it is a photolithography-type insulating paste or conductive paste, in order to minimize the number of parts to be removed by development, each paste is actually printed in a rough pattern, and then a high-definition pattern is formed by photolithography. A method of forming is also employed. Moreover, the method of forming a pattern by pattern printing is also considered, without using the photolithographic method for the photocurable resin composition.

  However, when the paste is printed in a pattern, if the actual paste pattern is too large compared to the pattern shape of the screen plate, problems such as mounting defects at the time of component mounting or short circuiting due to contact between conductors occur. This is called paste bleeding. One of the seepage of paste is that the amount of solvent in the paste is too large.

  On the other hand, if the amount of the solvent is reduced to suppress the seepage, the viscosity of the paste becomes too high, causing a problem that the paste is not transferred to the substrate during pattern printing. It was difficult to do.

  In addition, with the recent improvement in performance of electronic devices, the resistance to cracking of cured products has become important for both insulating pastes and conductive pastes. One of the methods for improving the crack resistance of the cured product is a method of highly filling the filler. However, the conventional resin material has a problem that when the filler is filled in a high amount, the viscosity of the paste is remarkably increased and the printability is poor.

  Therefore, an object of the present invention is to provide a photocurable resin composition that has excellent printability without bleeding or blurring during pattern printing and can form a cured product having excellent crack resistance. And a dry film having a resin layer obtained from the composition, a cured product thereof, and a printed wiring board having the cured product.

  As a result of intensive studies, the present inventors have found that an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is a material excellent in wettability with a filler, and a solvent when blended with a photocurable resin composition. It was possible to reduce the viscosity of the paste without blending a large amount of the resin, and it was found that it was excellent in printability while maintaining crack resistance even when the filler was highly filled, and the present invention was completed.

  That is, the photocurable composition of the present invention comprises (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C) a filler. It is.

  In the photocurable composition of the present invention, the blending amount of the (C) filler is preferably 70 to 95% by mass with respect to the total mass of the photocurable resin composition.

  In the photocurable composition of the present invention, the (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton preferably has a carboxyl group.

  In the photocurable composition of the present invention, the acid value of the epoxy (meth) acrylate having the (A) urethane bond and the bisphenol AD skeleton is preferably in the range of 40 to 250 mgKOH / g.

  In the photocurable composition of the present invention, the glass transition temperature of the epoxy (meth) acrylate having the (A) urethane bond and the bisphenol AD skeleton is preferably in the range of −10 to 60 ° C.

  The dry film of the present invention is characterized by having a resin layer obtained by applying the photocurable resin composition to the film and drying it.

  The cured product of the present invention is obtained by curing the photocurable resin composition or the resin layer of the dry film.

  The printed wiring board of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  According to the present invention, a photocurable resin composition capable of forming a cured product having excellent printability without bleeding or blurring 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 can be provided.

The photocurable resin composition of the present invention comprises (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C) a filler. is there. As a result of intensive studies by the present inventors, by using an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, a paste viscosity that does not cause bleeding and blurring without adding a large amount of solvent is obtained. I found out that I can. Further, when developability is imparted, for example, when the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group-containing resin, the Na ₂ CO ₃ concentration is about 0.2% by mass. It has been found that even when development is performed using a dilute alkaline developer, development residue generation is suppressed and resolution is also improved. This is probably because the urethane bond and the bisphenol AD skeleton exhibited high wettability with the filler. In addition, since it is developed with a dilute alkaline aqueous solution, it is possible to form an image with little damage to the exposed area, and further, the dissolution contrast for the alkaline developer in the exposed and unexposed areas is increased, resulting in improved resolution. Presumed to have been improved.

  Moreover, since the photocurable resin composition of this invention is excellent in printability, even if it is highly filled with a filler, in order to increase crack tolerance, electroconductivity, etc., it can contain a filler with a high compounding quantity.

  Moreover, it is preferable that the photocurable resin composition of this invention contains a thermosetting component. Conventionally, for example, in the case of a conductive paste, a cured product is formed by baking at a high temperature and is in close contact with the substrate. However, in recent years, it is also required that a cured product can be formed at a low temperature from the viewpoint of the selectivity of the substrate. . When a thermosetting component is blended in the photocurable resin composition of the present invention, a cured product having excellent adhesion can be formed even when cured at a low temperature.

  In this specification, (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions.

  Hereinafter, each component which can be contained in the photocurable resin composition of the present invention including optional components will be described.

[(A) Epoxy (meth) acrylate having urethane bond and bisphenol AD skeleton]
The photocurable resin composition of the present invention contains (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton. (A) The epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton may have a carboxyl group, and in that case, the photocurable resin composition of the present invention can be made into an alkali developing type. Moreover, even if it does not have a carboxyl group, it may be made into an alkali developing type by blending other alkali-soluble components. The bisphenol AD skeleton is also referred to as a bisphenol E skeleton in this technical field.

  (A) The method for synthesizing an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is not particularly limited. For example, a bisphenol obtained by adding a diol compound to a bisphenol AD epoxy resin and gradually adding a diisocyanate compound. An epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton can be obtained by further reacting the AD type epoxy urethane resin with glycidyl (meth) acrylate. In the present invention, as the component (A), a structure obtained by reacting a diol compound with a bisphenol AD type epoxy resin as described above and further reacting with a diisocyanate compound has a urethane bond and a bisphenol AD skeleton. Epoxy (meth) acrylate can be suitably used.

  Also, the synthesis method is not particularly limited when the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group, that is, when it is a carboxyl group-containing bisphenol AD type epoxy urethane (meth) acrylate resin. Can be obtained, for example, by reacting an acid anhydride with an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton. Since the carboxyl group-containing resin as described above has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible. 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. is there. The acid value of the carboxyl group-containing resin is preferably 40 mgKOH / g or more from the viewpoint of developability. On the other hand, if it is 250 mgKOH / g or less, it is preferable from the viewpoint of preventing the exposed portion from being dissolved by the developer and making the line unnecessarily thin, and the dissolution contrast between the exposed portion and the unexposed portion from being deteriorated.

  The weight average molecular weight of the epoxy (meth) acrylate having (A) urethane bond and bisphenol AD skeleton varies depending on the resin skeleton, but is generally 2,000 to 150,000, more preferably 5,000 to 100,000. Those within the range are preferred. A mass average molecular weight of 2,000 or more is preferable from the viewpoint of tack-free performance and the like, and in the case of an alkali development type, it is also preferable from the viewpoint of resolution. On the other hand, a mass average molecular weight of 150,000 or less is preferable from the viewpoint of storage stability and the like, and in the case of an alkali development type, it is also preferable from the viewpoint of developability. The weight average molecular weight can be measured by gel permeation chromatography.

  (A) It is preferable that the glass transition temperature of the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is within a range of −10 to 60 ° C. In the case of −10 ° C. or higher, the tack-free performance is more excellent. In the case of 60 ° C. or lower, the crack resistance becomes better. More preferably, it is 0-40 degreeC.

  The glass transition temperature of the epoxy (meth) acrylate having (A) urethane bond and bisphenol AD skeleton contained in the photocurable resin composition of the present invention can be determined by differential scanning calorimetry (DSC) measurement of the photosensitive component. In the examples of the present specification, measurement was performed using this method.

  (A) The epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton can be used alone or in combination of two or more.

  The photocurable resin composition of the present invention may contain other photocurable resins as long as the curing of the present invention is not inhibited.

[(B) Photopolymerization initiator]
(B) It does not specifically limit as a photoinitiator, For example, an oxime ester type, an acetophenone type, a benzoin type, a phosphine oxide type photoinitiator can be used.
In the present invention, the photopolymerization initiator (B) is an oxime ester polymerization initiator having a group represented by the following general formula (I) or an acetophenone series having a group represented by the following general formula (II). A photopolymerization initiator is preferred.

  In general formula (I), R1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  In the general formula (II), R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 6 to 12 carbon atoms, and R5 and R6 each independently represent a hydrogen atom, or An alkyl group having 1 to 6 carbon atoms is represented. Or R5 and R6 may combine to form a ring together with the nitrogen atom in the formula, and this ring may contain an ether bond. Specific examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- And [4- (4-morpholinyl) phenyl] -1-butanone.

  Among the oxime ester photopolymerization initiators, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, TOE-004 manufactured by Nippon Chemical Industry Co., Ltd. TR-PBG-304 manufactured by Electronic New Materials Co., etc. is preferable.

  As the acetophenone photopolymerization initiator having a group represented by the general formula (II), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and N, N-dimethylaminoacetophenone. Examples of commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 379EG manufactured by BASF Japan.

  (B) A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  (B) Although the compounding quantity of a photoinitiator is not specifically limited, Preferably it is 0.01-30 mass parts with respect to 100 mass parts of (A) epoxy (meth) acrylates which have a urethane bond and bisphenol AD frame | skeleton. Yes, more preferably in the range of 0.5 to 15 parts by mass. It is preferable from a viewpoint of photocurability, chemical resistance, etc. as it is 0.01 mass part or more. On the other hand, when it is 30 parts by mass or less, light absorption on the surface of the cured coating film by the photopolymerization initiator is controlled, and this is preferable from the viewpoint of improving the deep part curability.

[(C) filler]
(C) It does not specifically limit as a filler, A well-known and usual inorganic or organic filler can be used. The purpose of blending the filler (C) is not particularly limited, and may be for increasing the physical strength of the coating film or imparting conductivity. It is preferable to use a conductive filler when imparting conductivity, and a non-conductive filler when the photocurable resin composition of the present invention is used to form an insulating layer.

Any conductive filler can be used as long as it is a filler that imparts 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, and the like. Among these, Ag is preferable. These conductive fillers may be used in the form of the above component alone, but may be used in the form of an alloy or oxide. Further, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), or the like can also be used. The conductive filler may be carbon powder such as carbon black, graphite, or carbon nanotube. However, care should be taken because the light transmittance is lowered.

  The shape of the conductive filler is not particularly limited, but is preferably other than flakes, particularly preferably acicular or spherical. As a result, the light transmittance is improved, and when the photocurable resin composition is an alkali development type, a conductive circuit or electrode having excellent resolution can be formed.

  In order to form a fine line, the conductive filler preferably has a maximum particle size of 30 μm or less. By setting the maximum particle size to 30 μm or less, when the photocurable resin composition is an alkali development type, the resolution of the conductive circuit and the electrode is improved.

The conductive filler is an average particle diameter of 10 random conductive fillers observed at 10,000 times using an electron microscope (SEM), and the range is preferably 0.1 to 10 μm. . It is preferable from an electroconductive viewpoint that an average particle diameter is 0.1 micrometer or more. On the other hand, when the average particle size is 10 μm or less, it is preferable from the viewpoint of preventing clogging of the screen. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers in the average particle diameter measured by the micro track. The conductive filler is preferably 10 ⁻³ Ω · cm or less.

The non-conductive filler preferably has a non-conductive property with a volume resistivity (JIS K 6911) of 10 ¹⁰ Ω · cm or more. Examples of the non-conductive filler include silica such as amorphous silica, fused silica, spherical silica, barium sulfate, hydrotalcite, talc, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, aluminum hydroxide, silicon nitride. , Aluminum nitride, boron nitride, Neuburg silica particles and the like.

  (C) A filler can be used individually by 1 type or in combination of 2 or more types.

  (C) It is preferable that the compounding quantity of a filler is 70-95 mass% on the basis of the total mass in a photocurable resin composition, and it is more preferable that it is 70-90 mass%. When the blending amount of the filler is 70% by mass or more, it is preferable from the viewpoint of printability, and when a conductive filler is blended, it is also preferable from the viewpoint of conductivity. On the other hand, when 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 photo-curable resin composition of the present invention preferably uses a reactive diluent for crosslinking with light. As the reactive diluent, it is preferable to use a (meth) acrylate compound. The reactive diluent is preferably polyfunctional. The reason why polyfunctionality is preferable is that the photoreactivity is improved as compared with the case where the number of functional groups is one, and the resolution is excellent in the case of the alkali development type.

  Examples of the (meth) acrylate compound include polyfunctional (meth) acrylate monomers or oligomers (bifunctional or higher functional (meth) acrylate monomers or oligomers). Specific examples include conventionally known polyester (meth) acrylates, poly Examples include ether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent acrylates such as thyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; Polyurethane polyol such as polyester polyol is directly acrylated or urethane acrylate via diisocyanate And at least one of acrylates and melamine acrylates, and methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound reacted with a half urethane compound may be used as a reactive diluent. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  Especially, it is preferable to use a polyfunctional (meth) acrylate monomer, and especially a tetrafunctional (meth) acrylate monomer is preferable. Examples of the tetrafunctional (meth) acrylate monomer include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.

  A reactive diluent can be used individually by 1 type or in combination of 2 or more types.

  Although the compounding quantity of a reactive diluent is not specifically limited, It is 10-100 mass parts with respect to 100 mass parts of (A) epoxy (meth) acrylates which have a urethane bond and bisphenol AD frame | skeleton, More preferably, it is 20-80. The proportion of parts by mass is appropriate. In the case of 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 an alkaline aqueous solution is good, and the pattern film is not easily brittle.

(Thermosetting component)
The photocurable resin composition of the present invention preferably contains a thermosetting component because crack resistance is further improved. As thermosetting components used in the present invention, known and commonly used amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, etc. A thermosetting resin can be used. A thermosetting component can be used individually by 1 type or in combination of 2 or more types. In the present invention, the thermosetting component having at least one selected from the group consisting of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether group), or 1 A thermosetting component having two or more isocyanate groups or blocked isocyanate groups in the molecule is preferred.

  The thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. A compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound And compounds having two or more thioether groups in the molecule, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include JER828, JER834, JER1001, JER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152 and Epicron 165 manufactured by DIC, Epototo YDB-400 and YDB-500 manufactured by Tohto Kasei Co., Ltd., and D.C. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714; JER152 and JER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak-type epoxy resins such as ECN-235 and ECN-299; epphenol 830 manufactured by DIC, JER807 manufactured by Mitsubishi Chemical, Epototo YDF-170, YDF-175 and YDF-2004 manufactured by Toto Kasei Resin: Hydrogenated bisphenol A type epoxy resin such as Epototo ST-2004, ST-2007, ST-3000 manufactured by Toto Kasei Co., Ltd .; JER604 manufactured by Mitsubishi Chemical Corporation, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as Sumi-Epoxy ELM-120 manufactured by Hydant-in type epoxy resin; Alicyclic epoxy resin such as Celoxide 2021P manufactured by Daicel Corporation; YL-933 manufactured by Mitsubishi Chemical Corporation, T manufactured by Dow Chemical Company . E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502; Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000 and YL-6121 manufactured by Mitsubishi Chemical Corporation, or mixtures thereof; Japan Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayaku Co., Ltd. EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC, etc .; Bisphenol A novolac type epoxy resin such as JER157S manufactured by Mitsubishi Chemical; Tetraphenylolethane type epoxy resin such as JERRY-931; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries; diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; ZX-1063 manufactured by Tohto Kasei Co., Ltd. Tetraglycidyl xylenoe Resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphtalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC, etc .; Dimers such as HP-7200, HP-7200H manufactured by DIC, etc. Epoxy resin having cyclopentadiene skeleton; CP-50S, CP-50M glycidyl methacrylate copolymer epoxy resin such as Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative ( Examples include, but are not limited to, e.g., Epode PB-3600 manufactured by Daicel Corporation) and CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.). These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  In addition, in the photocurable resin composition of the present invention, in order to improve the curability of the photocurable resin composition and the toughness of the resulting cured film, two or more isocyanate groups in one molecule, or blocked. It is preferable to add a compound having an isocyanate group. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two in one molecule. Examples thereof include compounds having the above blocked isocyanate groups, that is, blocked isocyanate compounds.

  As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  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 this isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

  Examples of isocyanate blocking agents include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam. Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents and the like.

  The block isocyanate compound may be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, manufactured by Baxenden) Sumijour BL-3175, BL-4165, BL-1100 , BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (above, 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, E 402-B80T, MF-B60B, MF-K60B, SBN-70D (Asahi Kasei Co., Ltd.), Karenz MOI-BM (Showa Denko Co., Ltd.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The compounding amount of such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is based on (A) 100 parts by mass of epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton. A ratio of 1 to 100 parts by mass, more preferably 2 to 70 parts by mass is appropriate. It is preferable from a viewpoint of the toughness of a coating film as it is 1 mass part or more. On the other hand, it is preferable from a viewpoint of storage stability that it is 100 mass parts or less.

  The photocurable resin composition of the present invention is exemplified below together with the above-described components in order to further improve the effects of the present invention or to exhibit further effects within a range not inhibiting the effects of the present invention. Other ingredients may be included.

(Organic acid)
As the organic acid, an organic acid having no aromatic ring is preferable. By blending an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself is suppressed, and the photoreactivity of the epoxy (meth) acrylate having a (A) urethane bond and a bisphenol AD skeleton is relatively improved. And excellent resolution can be obtained. Of these, dicarboxylic acids are preferred, and 2,2′-thiodiacetic acid is more preferred.

Specific examples of organic acids include 2,2′-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, malonic acid, butyric acid, Carboxylic acids such as malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid; dibutyl phosphite, butyl phosphite, dimethyl phosphite, methyl phosphite, phosphorous acid Mono- or diesters of phosphorous acid such as dipropyl, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, phosphite-n-methyl-2-ethylhexyl; phosphorus Dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, Examples thereof include mono- and diesters of phosphoric acid such as diisopropyl phosphate, isopropyl phosphate, and phosphoric acid-n-butyl-2-ethylhexyl.

  The amount of the organic acid is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy (meth) acrylate having the (A) urethane bond and bisphenol AD skeleton. In the case of 1 part by mass or more, the developability becomes better, while in the case of 10 parts by mass or less, the resolution is excellent.

(Dispersant)
By mix | blending a dispersing agent, the dispersibility and sedimentation property of a photocurable resin composition can be improved.

  Examples of the dispersing agent include, 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, DISPERBY63-62 -164, DISPERBYK- 66, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBY92 DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-150P, DISPERBYK-2150 -P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (manufactured by BYK Japan), Disparon 2150, Disparon 1210, Disparon KS-860, Disparon KS-873N, Disparon 7004, Disparon 1830, Disparon 1860 , Disparon 1850, Disparon DA-400N, Disparon PW-36, Disparon DA-703-50 (manufactured by Enomoto Kasei), Floren G-450, Floren G-600, Floren G-820, Floren G-700, Floren DOPA- 44, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The content of the dispersant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the filler in order to effectively achieve the above object.

(Photopolymerization inhibitor)
By adding a photopolymerization inhibitor, it is possible to suppress a certain amount of radical polymerization in accordance with the type and amount of the polymerization inhibitor among radical polymerization that occurs inside the photocurable resin composition by exposure. Thereby, the photoreaction with respect to weak light like scattered light can be suppressed. Therefore, a finer conductive circuit line can be formed sharply and can be preferably used. The photopolymerization inhibitor is not particularly limited as long as it can be used as a photopolymerization inhibitor. For example, p-benzoquinone, naphthoquinone, di-t-butyl paracresol, hydroquinone monomethyl ether, α-naphthol, acetanidin Acetate, hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid, quinone dioxime, pyrogallol, tannic acid, resormin, cuperone, phenothiazine and the like can be mentioned.

(Thermosetting catalyst)
When using the thermosetting component which has a 2 or more cyclic (thio) ether group in the said molecule | numerator in the photocurable resin composition of this invention, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N manufactured by San Apro, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it promotes the reaction of a carboxyl group with at least one selected from a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and an oxetanyl group, You may use individually by 1 type or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing resin or thermosetting component having two or more cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.

(Thermal polymerization inhibitor)
The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the photocurable resin composition of the present invention. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, chloranil, naphthylamine. , Β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine , Methylene blue, copper and organic chelating agent reactant, methyl salicylate, and nitroso compounds, chelate of nitroso compounds and Al, and the like.

(Chain transfer agent)
In the photocurable resin composition of the present invention, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, B pentane thiol, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate) can be used.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz -NR1 (above, Showa Denko Co., Ltd.) etc. can be mentioned.

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, 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-hexanolactam, 2 , 4,6-trimercapto-s-triazine (Dysnet F from Sankyo Kasei), 2-dibutylamino-4,6-dimercapto-s-triazine (Disnet DB from Sankyo Kasei), and 2-anilino- Examples include 4,6-dimercapto-s-triazine (Dysnet AF manufactured by Sankyo Kasei Co., Ltd.).

  In particular, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (Kawaguchi Chemical Co., Ltd.) is a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition. Axel M manufactured by Kogyo Co., Ltd.), 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H -Tetrazole is preferred. These chain transfer agents can be used alone or in combination of two or more.

(Other additive components)
The photocurable resin composition of the present invention requires known and commonly used components such as thickeners, antifoaming / leveling agents, coupling agents, antioxidants, rust inhibitors, colorants, organic solvents, etc. Of course, it can mix | blend suitably according to.

  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-component or two-component or more. When forming into a dry film, the resin layer obtained by apply | coating and drying the photocurable resin composition of this invention on a film is formed. After forming the resin layer, it is preferable to laminate a peelable film on the surface of the membrane for the purpose of preventing dust from adhering to the surface of the membrane.

(Formation of photocured coating)
(A) When the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton has a carboxyl group, patterning is possible by a photolithography method. Below, an example of the method of forming a photocurable coating film with the photolithographic method using the photocurable resin composition of this invention is demonstrated.

  In the photocurable resin composition of the present invention, a machine such as a three-roll roll or a blender is used for kneading and dispersing the above-described essential components and optional components. The photocurable resin composition thus dispersed is applied onto the substrate by an appropriate application method such as a screen printing method, a bar coater, or a blade coater.

  After coating, it is preferable to dry the coating film in order to obtain touch dryness. The drying method is not particularly limited. For example, in a hot air circulation drying furnace, a far-infrared drying furnace, etc., the (A) epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is dried at about 60 to 120 ° C. for about 5 to 40 minutes. The tacky-free coating film is obtained by evaporating the organic solvent.

Next, contact exposure or non-contact exposure is performed using a negative mask having a predetermined exposure pattern. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. As the exposure amount, the integrated light amount can be a low light amount of 200 mJ / cm ² or less. In addition, you may form a pattern in a coating film with a laser direct imaging apparatus, without using a mask.

  Next, the coating film is formed into a pattern by development such as spraying or dipping. As the developer, an aqueous metal alkali solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium silicate, or an aqueous amine solution such as monoethanolamine, diethanolamine, or triethanolamine can be used. In particular, a dilute alkaline aqueous solution having a concentration of about 1.5% by mass or less is preferably used as long as the carboxyl group in the photocurable resin composition is saponified and the uncured part (unexposed part) is removed. The developer is not limited to the above.

  According to the photocurable resin composition of the present invention, the use of a dilute alkaline aqueous solution as a developer causes little damage to the coating film, and does not cause a problem of development residue, and has excellent resolution. A cured coating film can be obtained.

Accordingly, in one aspect of the present invention, a developing solution used in the method of forming a photocured coating is preferably _Na 2 CO ₃ concentration of a dilute aqueous alkaline solution of 0.1 to 2.0 wt%, Na ₂ A dilute alkaline aqueous solution having a CO ₃ concentration of 0.2 to 1.0% by mass is more preferable.

  After development, it is preferable to perform water washing and acid neutralization in order to remove unnecessary developer.

  The obtained photocured coating film is cured at a temperature at which (A) the epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton is not thermally decomposed. Thereby, the cured coating film which is excellent in printability, and excellent in adhesiveness and crack resistance can be formed. As thermosetting temperature, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, 140 degrees C or less is more preferable, 130 degrees C or less is especially preferable.

  In these steps, a resin base material having no heat resistance can be used as the base material. Specifically, as a resin base material, for example, polyimide, polyester resin, polyethersulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide (PA) , Polypropylene (PP), polyphenylene oxide (PPO), and the like, and a polyester-based resin can be preferably used. A glass substrate or the like may be used. In addition to the printed wiring board and the flexible printed wiring board that have been previously formed with copper or the like as the substrate, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / It uses materials such as paper epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, etc., copper-clad laminates for high-frequency circuits, and all grades (FR-4 etc.) of copper In addition, a tension laminate, a glass substrate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a ceramic substrate, a wafer plate, or the like may be used.

  The photocurable resin composition of the present invention is suitably used for conductive circuits, electrodes, electromagnetic wave shield formation, conductive adhesives, etc., and for forming a cured film on a printed wiring board, that is, a printed wiring board. It is also preferably used for forming a permanent film, more preferably used for forming a solder resist or coverlay or an interlayer insulating material. Particularly preferably, it is used for forming a solder resist, that is, as a solder resist composition. In addition, you may use the photocurable resin composition of this invention in order to form a solder dam.

  The present invention will be specifically described below based on examples. However, the present invention is not limited to these examples.

<Synthesis of epoxy acrylate (A-1) having urethane bond and bisphenol AD skeleton>
Bisphenol AD type epoxy resin R-710 (Mitsui Chemicals): 174 g (0.5 mol) was dissolved in carbitol acetate: 500 mL, and 2-methylhydroquinone: 0.5 g and 1,6- Hexanediol: 142 g (1.2 mol) was added, and the temperature was raised to 45 ° C. To this solution, 202 g (1.2 mol) of hexamethylene diisocyanate was added as a diisocyanate compound, which was gradually added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the mixture was reacted for 6 hours until absorption near 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method. 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 is raised to 95 ° C. and reacted for 6 hours to give an epoxy having a urethane bond and a bisphenol AD skeleton. A resin solution of acrylate (A-1) was obtained. The solid content was 55% by mass, and the Tg obtained from DSC measurement was 25.3 ° C.

<Synthesis of epoxy acrylate (A-2) having urethane bond and bisphenol AD skeleton>
Resin of epoxy acrylate (A-2) having a urethane bond and a bisphenol AD skeleton, reacted under the same conditions as in (A-2) except that 267 g (1.2 mol) of isophorone diisocyanate was used as the diisocyanate compound. A solution was obtained. The solid content was 50% by mass, and the Tg obtained from DSC measurement was 26.5 ° C.

<Synthesis of epoxy acrylate (A-3) having a carboxyl group and having a urethane bond and a bisphenol AD skeleton>
As an epoxy acrylate having a urethane bond and a bisphenol AD skeleton, a 53 wt% solution of (A-1): 433 g, triphenylphosphine: 0.5 g and tetrahydrophthalic anhydride: 183 g (1.2 mol) are charged and stirred. The reaction was carried out at 110 ° C. for 5 hours. As a result, a resin solution of epoxy acrylate (A-3) having a carboxyl group and having a urethane bond and a bisphenol AD skeleton was obtained. The solid content was 51 mass%, the solid content acid value was 85 mgKOH / g, and the Tg obtained from DSC measurement was 19.2 ° C.

<Synthesis of epoxy acrylate (A-4) having a carboxyl group and having a urethane bond and a bisphenol AD skeleton>
The reaction is carried out under the same conditions as in the method (A-3) except that 476 g of a 50% by weight solution of (A-2) is used as an epoxy acrylate having a urethane bond and a bisphenol AD skeleton. An epoxy acrylate (A-4) resin solution having a urethane bond and a bisphenol AD skeleton was obtained. The solid content was 53 mass%, the solid content acid value was 82 mgKOH / g, and the Tg obtained from DSC measurement was 21.3 ° C.

  Here, an acid value means the value measured by the following method according to the method as described in "JIS K 2501-2003 petroleum product and lubricating oil-neutralization number test method." The same applies to the acid value described later.

[Measurement method of acid value]
The sample is dissolved in a titration solvent in which xylene and dimethylformamide are mixed at a mass ratio of 1: 1, and titrated with a 0.1 mol / L potassium hydroxide / ethanol solution by potentiometric titration. The inflection point on the titration curve is the end point, and the acid value is calculated from the titration amount up to the end point of the potassium hydroxide solution.

[Preparation of Photocurable Resin Composition]
Each component described in Tables 1 and 2 below was blended and stirred, and three passes were performed using a three-roll mill. Thereafter, carbitol acetate was added as a solvent so that the paste viscosity would be 250 dPa · s ± 20 Pa · s to obtain each photocurable resin composition described in the same table.

  <Evaluation method>

(viscosity)
Each photocurable fat composition produced according to the above [Preparation of photocurable resin composition] was used at 25 ° C. using a cone plate viscometer TVE-33H manufactured by Toki Sangyo Co., Ltd., cone rotor shape 3 ° R9.7. The viscosity at a cone rotor rotational speed of 5 rpm was measured.

(Leaking out and scraping evaluation specimen preparation method)
The photo-curable resin composition described in Tables 1 and 2 below was washed with water after buffing and dried, and was dried on a glass epoxy substrate having a thickness of 1.6 mmt with a line and space (L / S) of 380 mesh and 100 μm / 100 μm. Using a SUS calendar plate, a pattern was applied so that the film thickness after drying was 5 μm, and then dried in a hot-air circulating drying oven at 80 ° C. for 30 minutes to produce a test piece with good touch drying properties. .

(Leaking out)
The test piece produced by the above method was observed using an optical microscope, and the amount of bleeding was calculated from the following formula (1) and evaluated.
Exudation amount (μm) = actual pattern width (μm) −100 μm (1)

(Scratch)
The test piece produced by the said method was observed visually, and the degree of the blur of a dry coating film was evaluated.
○: No dullness on the dried coating film.
(Triangle | delta): There exists some blurring in a dry coating film.
X: There is a clear blur in the dried coating film.

(Test specimen preparation method for evaluation of adhesion and crack resistance)
The photo-curable resin composition described in Tables 1 and 2 below was washed with water after buffing and dried, and was dried on a glass epoxy substrate having a thickness of 1.6 mmt with a line and space (L / S) of 380 mesh and 100 μm / 100 μm. It applied so that the film thickness after drying might be set to 5 micrometers using the SUS calendar plate, and it dried for 30 minutes at 80 degreeC in the hot-air circulation type drying furnace, and formed the coating film with favorable touch-drying property. Thereafter, a high-pressure mercury lamp was used as the light source, and the entire surface was exposed so that the integrated light amount on each photocurable resin composition was 500 mJ / cm ² . Finally, it was cured at 150 ° C. for 60 minutes to prepare a test piece for evaluating adhesion and crack resistance.

(Adhesion)
A cellotape (registered trademark) peel was applied to the line and space (L / S) of L / S = 100/100 μm produced by the above method, and the adhesion was evaluated.
○: No line loss.
Δ: There is a slight line defect.
×: There is a significant loss of lines.

(Crack resistance)
The test piece produced by the above method was bent so that the pattern alternated between the inner side and the outer side and returned to its original state, and the presence or absence of cracks was observed and evaluated.
(Double-circle): There is no crack even if a bending operation is repeated 30 times or more.
○: Cracking occurs when the bending operation is 20 times or more and less than 30 times.
(Triangle | delta): A bending operation | movement is 10 times or more and less than 20 times, and there exists a crack.
X: The bending operation is less than 10 times and there is a crack.

(Test piece preparation method for resolution evaluation)
Among the photocurable resin compositions shown in Tables 1 and 2 below, a glass epoxy substrate having a plate thickness of 1.6 mmt obtained by washing a photocurable resin composition containing a carboxyl group-containing epoxy acrylate with water after buffing and drying and drying. Using a 380-mesh SUS calender plate, the whole surface was coated so that the film thickness after drying was 5 μm, and then dried in a hot-air circulating drying oven at 80 ° C. for 30 minutes for good touch drying properties. A coating film was formed. Then, using a high pressure mercury lamp as a light source, pattern exposure was performed so that the integrated light amount on each photocurable resin composition was 500 mJ / cm ² through a 30 μm / 40 μm line and space (L / S) negative mask. . Then, the liquid temperature 30 ℃, _Na 2 CO ₃ concentration then developed using a 0.2 wt% sodium carbonate aqueous solution, and washed with water. Finally, it was cured at 150 ° C. for 60 minutes to prepare a test piece for evaluation of resolution.

(Resolution)
The resolution was evaluated in a 30 μm / 40 μm line and space (L / S) of the test piece.
○: No line loss.
Δ: Slightly missing line
×: There is a significant loss of lines.

  Tables 1 and 2 summarize the test results. In addition, what is not attached | subjected with the numerical value regarding each component in Table 1 and 2 shows a mass part.

＊１：Ａ−１、ウレタン結合およびビスフェノールＡＤ骨格を有するエポキシ（メタ）アクリレート、固形分５５質量％、表中の配合量は樹脂溶液の配合量
＊２：Ａ−２、ウレタン結合およびビスフェノールＡＤ骨格を有するエポキシ（メタ）アクリレート、固形分５０質量％、表中の配合量は樹脂溶液の配合量
＊３：Ａ−３、カルボキシル基を有し、ウレタン結合およびビスフェノールＡＤ骨格を有するエポキシ（メタ）アクリレート、固形分５１質量％、固形分酸価８５ｍｇＫＯＨ／ｇ、表中の配合量は樹脂溶液の配合量
＊４：Ａ−４、カルボキシル基を有し、ウレタン結合およびビスフェノールＡＤ骨格を有するエポキシ（メタ）アクリレート、固形分５３質量％、固形分酸価８２ｍｇＫＯＨ／ｇ、表中の配合量は樹脂溶液の配合量
＊５：ＫＡＹＡＲＡＤ ＵＸＥ−３０００、日本化薬社製カルボキシル基含有ビスフェノールＡ型ウレタンエポキシアクリレート、固形分６５質量％、固形分酸価１００ｍｇＫＯＨ／ｇ、表中の配合量は樹脂溶液の配合量
＊６：ＫＡＹＡＲＡＤ ＺＦＲ−１４０１Ｈ、日本化薬社製カルボキシル基含有ビスフェノールＡ型エポキシアクリレート、固形分６３質量％、固形分酸価１００ｍｇＫＯＨ／ｇ、表中の配合量は樹脂溶液の配合量
＊７：フィラー、堺化学工業社製バリエースＢ−３０、硫酸バリウム
＊８：フィラー、龍森社製ＦＵＳＥＬＥＸ ＷＸ、シリカ
＊９：フィラー、昭和電工社製Ａ−５０−Ｋ、アルミナ
＊１０：フィラー、石原産業社製タイペークＣＲ−９７、酸化チタン
＊１１：フィラー、ＤＯＷＡエレクトロニクス社製ＡＧ３−８Ｆ、銀粉
＊１２：光重合開始剤、ＢＡＳＦジャパン社製ＩＲＧＡＣＵＲＥ ＯＸＥ０２
＊１３：光重合開始剤、ＢＡＳＦジャパン社製ＩＲＧＡＣＵＲＥ ９０７
＊１４：反応性希釈剤、新中村化学工業社製ＮＫオリゴＵ−４ＨＡ、４官能ウレタンアクリレート
＊１５：反応性希釈剤、日本化学社製ＫＡＹＡＲＡＤ ＴＭＰＴＡ、トリメチロールプロパントリアクリレート
＊１６：反応性希釈剤、新中村化学社製ＮＫエステルＡ−ＴＭＭＴ、ペンタエリスリトールテトラアアクリレート、
＊１７：反応性希釈剤、日本化学社製ＫＡＹＡＲＡＤ ＤＰＨＡ、ジペンタエリスリトールヘキサアクリレート
＊１８：熱硬化性成分、三菱化学社製ＪＥＲ８２８、ビスフェノールＡ型エポキシ樹脂
＊１９：熱硬化性成分、旭化成社製ＤＵＲＡＮＡＴＥ ＭＦ−Ｂ６０Ｂ、ブロックイソシアネート
＊２０：分散剤、ビックケミー・ジャパン社製ＤＩＳＰＥＲＢＹＫ−１９１
＊２１：有機酸、関東化学社製 ２，２'−チオ二酢酸
＊２２：溶剤、出光興産社製イプゾール１５０、石油系溶剤

* 1: A-1, epoxy (meth) acrylate having urethane bond and bisphenol AD skeleton, solid content 55% by mass, blending amount in table is blending amount of resin solution * 2: A-2, urethane bond and bisphenol AD Epoxy (meth) acrylate having a skeleton, solid content 50% by mass, blending amount in the table is blending amount of resin solution * 3: A-3, epoxy having a carboxyl group, urethane bond and bisphenol AD skeleton (meta ) Acrylate, solid content 51% by mass, solid content acid value 85 mgKOH / g, blending amount in table is blending amount of resin solution * 4: A-4, epoxy having carboxyl group, urethane bond and bisphenol AD skeleton (Meth) acrylate, solid content 53 mass%, solid content acid value 82 mgKOH / g, blending amount in table is blending amount of resin solution * : KAYARAD UXE-3000, Nippon Kayaku Co., Ltd. carboxyl group-containing bisphenol A type urethane epoxy acrylate, solid content 65 mass%, solid content acid value 100 mgKOH / g, compounding amount in the table is compounding amount of resin solution * 6: KAYARAD ZFR-1401H, Nippon Kayaku Co., Ltd. carboxyl group-containing bisphenol A type epoxy acrylate, solid content 63% by mass, solid content acid value 100 mgKOH / g, the compounding amount in the table is the compounding amount of the resin solution * 7: filler, Sakai Chemical VARIACE B-30 manufactured by Kogyo Co., Ltd., barium sulfate * 8: filler, FUSELEX WX manufactured by Tatsumori Co., Ltd., silica * 9: filler, A-50-K manufactured by Showa Denko KK, alumina * 10: filler, Taipei CR manufactured by Ishihara Sangyo -97, titanium oxide * 11: filler, AG3-8 manufactured by DOWA Electronics , Silver powder * 12: light polymerization initiator, manufactured by BASF Japan Ltd. IRGACURE OXE02
* 13: Photopolymerization initiator, IRGACURE 907 manufactured by BASF Japan
* 14: Reactive diluent, NK Oligo U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd., tetrafunctional urethane acrylate * 15: Reactive diluent, KAYARAD TMPTA, trimethylolpropane triacrylate manufactured by Nippon Chemical Co., Ltd. * 16: Reactive dilution Agent, Shin Nakamura Chemical Co., Ltd. NK ester A-TMMT, pentaerythritol tetraacrylate,
* 17: Reactive diluent, KAYARAD DPHA manufactured by Nippon Chemical Co., Ltd., dipentaerythritol hexaacrylate * 18: Thermosetting component, JER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin * 19: Thermosetting component, manufactured by Asahi Kasei Corporation DURANATE MF-B60B, blocked isocyanate * 20: dispersant, DISPERBYK-191 manufactured by Big Chemie Japan
* 21: Organic acid, 2,2'-thiodiacetic acid manufactured by Kanto Chemical Co., Ltd. * 22: Solvent, Ipsol 150 manufactured by Idemitsu Kosan Co., Ltd., petroleum solvent

  From the results shown in the above table, the photo-curable resin composition of the present invention can form a cured product having excellent printability without exudation and blurring and having excellent crack resistance. It turns out that it is possible.

Claims (8)

  A photocurable resin composition comprising (A) an epoxy (meth) acrylate having a urethane bond and a bisphenol AD skeleton, (B) a photopolymerization initiator, and (C) a filler.   The compounding quantity of the said (C) filler is 70-95 mass% with respect to the total mass of a photocurable resin composition, The photocurable resin composition characterized by the above-mentioned.   The photocurable resin composition according to claim 1 or 2, wherein the epoxy (meth) acrylate having (A) a urethane bond and a bisphenol AD skeleton has a carboxyl group.   4. The photocurable resin composition according to claim 3, wherein the acid value of the epoxy (meth) acrylate having the (A) urethane bond and the bisphenol AD skeleton is in the range of 40 to 250 mgKOH / g.   The glass transition temperature of the epoxy (meth) acrylate having the (A) urethane bond and the bisphenol AD skeleton is in the range of -10 to 60 ° C. The light according to any one of claims 1 to 4, Curable resin composition.   It has a resin layer obtained by apply | coating and drying the photocurable resin composition as described in any one of Claims 1-5 on a film, The dry film characterized by the above-mentioned.   Hardened | cured material obtained by hardening the resin layer of the photocurable resin composition as described in any one of Claims 1-5, or the dry film of Claim 6.   A printed wiring board comprising the cured product according to claim 7.