TW201105720A - Curable resin composition, dry film and printed circuit board using the same - Google Patents

Abstract

The invention provides a curable resin composition including a halogen-free flame retardant, which is a curable resin composition that can form a solder resist layer of low warping property and has excellent performance in flame retardance, and bending property; the dry film thereof, and the printed circuit board formed by the curable resin composition as the flame retardant cured film such as the solder resist. The curable resin composition according to this invention includes (A) a resin including a carboxyl group, (B) aluminum hydroxide, and (C) true sphere-shaped silicon dioxide. Besides the aforementioned components, this curable resin composition further includes (D) thermal curable component including two or more cyclic ether groups and/or cyclic thioether groups so as to be a thermal curable resin composition, and the thermal curable resin composition further includes (F) light polymerization initiator and (G) light polymerization monomer so as to be a light and thermal curable resin composition, and more preferably further includes (E)

Description

201105720 VI. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a curable resin composition, and more particularly to a hardenability of a solder resist which can form low warpage and which is excellent in flame retardancy and flexibility. Resin composition. Further, the present invention relates to a dry film and a flame-retardant printed wiring board using the curable resin composition. [Prior Art] Conventionally, a printed wiring board and a flexible wiring board (hereinafter abbreviated as FPC) are required to be flame-retardant in order to be mounted on an electronic machine, and are also known as solder resists belonging to such a part. It is required to be flame retardant. Among them, the FPC is generally a film different from the printed wiring board of the glass epoxy substrate due to the formation of the polyimide substrate. However, since the solder resist to be applied is the same film thickness because of the printed wiring board and the FPC, the burden of the flame retardant of the solder resist is relatively large when the film is FPC. Therefore, there have been various proposals for the flame retardancy of solder resists in the past. For example, JP-A-2007-1 0794 (Patent Document 1) proposes a flame-retardant photosensitive resin composition for FPC containing (a) a binder polymer and (b) a bromine in a molecule. a photopolymerizable compound which is a polymerizable ethylenically unsaturated bond such as a halogenated aromatic ring such as a phenyl group or a (meth) acrylonitrile group; (c) a photopolymerization initiator; (d) a blocked isocyanate compound; (e) A phosphorus-containing compound having a phosphorus atom in the molecule. However, if a compound having a halogenated aromatic ring and a polymerizable unsaturated double bond is used, the use of the halogen compound is not preferable from the viewpoint of environmental load. -5- 201105720 Therefore, the recent solder resist is replaced with the green colorant anthocyanin green from the viewpoint of reducing the environmental load, and is colored with anthocyanin blue and yellow which do not have a halogen atom. The solder resist of the agent is popular (for example, refer to Patent Document 2). Further, in order to clearly claim the halogen-free claim from the appearance, anthraquinone blue was used as a direct blue resist. However, although the solder resist is formed to protect the copper circuit, the other side has the role of making the heat or moisture of the copper circuit 'electrical discoloration or scratches, dirt, etc. on the copper circuit invisible (concealing). . In this regard, the solder resist is usually added with a coloring agent, and it is difficult to see the appearance defect due to the concentration of the solder. However, compared to the green color caused by the anthraquinone green, the blue solder resist ink or the green solder resist ink caused by the blue colorant and the yellow colorant is less concealed and has no It can be used as a function that can sufficiently realize a coloring agent which is difficult to see in appearance. Further, in the printed circuit board of the film represented by FPC, there is a problem that warpage due to hardening shrinkage occurs when the solder resist is photocured or thermally cured. However, aluminum hydroxide is a flame retardant material, and it is known that when it is added to a resin composition, the more it is added, the more the composition becomes flame retardant. However, the shape of the aluminum hydroxide is indefinite, and excessive addition causes cracks in the interface between the aluminum hydroxide and the resin as a starting point, and there is a problem that the bending resistance of the hardened film is lowered. Therefore, a printed wiring board having a flexible property is required, and in particular, a solder resist for an FPC board is limited in its amount of addition. In addition, in the method of preventing cracks at the interface between organic matter and inorganic matter, 201105720 is a method for raising organic matter, and a method for raising the affinity of inorganic particles is known, and in the past, a sand courtyard affinity agent treatment was performed. Acid ester and aluminum chelation (alumichelate) treatment and the like. However, such an affinity-advancing method has little effect on aluminum hydroxide, and in the present state, it is almost impossible to obtain an effect of improving the bending of the hardened film. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2007-1 0794 (Scope of Patent Request) [Patent Document 2] JP-A-2000-7974 (Scope of Patent Request) [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made to solve the problems of the prior art as described above, and a main object thereof is to provide a curable resin composition containing a halogen-free flame retardant. It is a curable resin composition which is low-warpage and can form a solder resist layer which is resistant to bending. In addition, the object of the present invention is to provide a dry film which is low in warpage and excellent in flame retardancy and flexibility and a flame retardant film having such excellent characteristics by using the curable resin composition. Printed wiring board. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a hardened 201105720 resin composition characterized by (A) a carboxyl group-containing resin, (B) aluminum hydroxide, and (C) a true ball. Ascerium dioxide. In the same manner, in addition to the above-mentioned respective components, the thermosetting resin having two or more cyclic ether groups and/or cyclic thioether groups in the molecule (D) may be further contained, and the thermosetting resin may be used. Composition. In other preferred embodiments, the (E) phosphorus-containing compound is further contained. In other cases, the photocurable thermosetting resin composition can be formed by further containing (F) a photopolymerization initiator and (G) a photopolymerizable monomer. In other preferred embodiments, the colorant (H) may be further contained. More preferably, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure or a carboxyl group-containing resin having a biphenyl aldehyde structure and an ethylenically unsaturated group, and further, in the above molecule The thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups is an epoxy resin having a biphenol aldehyde skeleton. Such a curable resin composition can be applied to the formation of a solder resist of a printed wiring board. Further, according to the present invention, it is possible to provide a dry film obtained by applying the curable resin composition to a film, or to apply the curable resin composition or the curable resin composition to a carrier film. The dried film obtained by drying it is subjected to heat hardening and/or photohardening to obtain a cured product. Further, according to the present invention, it is also possible to provide a printed wiring board having the above cured product. [Effects of the Invention] The curable resin composition of the present invention contains (A) a carboxyl group-containing resin and contains (B) aluminum hydroxide and (C) true spherical ceria, and by -8-201105720 It is preferable to further contain (E) a phosphorus-containing compound, and a non-halogen (nonhalo gen) composition can form a film which exhibits less environmental load, is flame retardant, and exhibits excellent low warpage and flexibility. Therefore, by using the curable resin composition of the present invention, it is possible to provide a dry film which is low in warpage and excellent in flame retardancy and flexibility, and a printing of a flame retardant solder resist film having such excellent characteristics. Wiring board. [Embodiment] The present invention has been repeatedly studied for the purpose of solving the above problems. The cerium oxide (C) and the aluminum hydroxide (B) which is a flame retardant material maintain the flame retardancy of the curable resin composition and improve the bending resistance. In particular, since the true spherical cerium oxide does not have a surface which becomes the starting point of the crack of the hardened film, the effect of improving the bending resistance directly is obtained. Further, the surface treatment by a decane coupling agent or the like has a very effective effect on cerium oxide, and the bending resistance can be lifted upwards drastically. This effect is an amazing effect that has never been considered before. Hereinafter, each constituent component of the curable resin composition of the present invention will be described in detail. In the resin (A) containing a carboxyl group contained in the curable resin composition of the present invention, a conventionally known resin compound containing a carboxyl group in the molecule can be used. Further, when it is a resin composition of an alkali-developing property, it is a carboxyl group-containing photosensitive resin (A' having an ethylenically unsaturated double bond in the molecule from the viewpoint of photocurability or development resistance (A'). ) Better. Further, those which are unsaturated acrylic or methacrylic acid derivatives are preferred. Further, when only a carboxyl group-containing resin having an ethylenically unsaturated double bond is used, it is necessary to use a photopolymerizable monomer (G) having two or more ethylene-saturation groups in the molecule to be described later in order to make the photocurability. As a specific example of the carboxyl group-containing resin (A), it is preferred to use the exemplified compounds (oligomer and (poly) polymer). (1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated compound such as styrene, α-methylethylene, lower alkyl (meth) acrylate or isobutylene. (2) A carboxyl group such as an aliphatic diisocyanate 'different aliphatic diisocyanate cyclic diisocyanate or an aromatic diisocyanate such as dihydroxymethyl diisocyanate or dimethyl methyl butyrate Glycolized, polycarbonate-based polyol, polyether-based polyol, polyester-based polyol olefin-based polyol, acrylic polyol, bisphenol-based alkylene oxide diol, phenolic hydroxyl group and alcohol A compound containing a hydroxyl group or the like is subjected to a sequential addition reaction to obtain a carboxyl group-containing urethane. (3) A diisocyanate compound such as an aliphatic diisocyanate, a divalent aliphatic diisoester, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, and a polyester An amino acid obtained by successive addition reaction of an alcohol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A oxyalkylene adduct diol, a diol compound having a phenolic hydroxyl group and an alcoholic hydroxyl group The ester is derived from an ester of an unsubstituted phenyl group, an ester and a compound, a polyhydrocarbyl glycolate cyanate cyanide multi-line cyclate resin, 10-201105720, which is formed by reacting an acid anhydride. A carboxyl group-containing urethane resin at the end. (4) Diisocyanate and bisphenol A type epoxy resin 'hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, double Photosensitive carboxyl group-containing (meth) acrylate of a bifunctional epoxy resin such as a phenol epoxy resin or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound by sequential addition reaction A urethane resin. (5) In the resin synthesis of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. A carboxyl group-containing urethane resin formed by terminal (meth) acrylate. (6) In the resin synthesis of the above (2) or (4), one or more isocyanate groups and one or more molecules are added to the molecule such as a molar reaction product such as isophorone diisocyanate and pentaerythritol triacrylate. A compound of an acrylonitrile group, which is a terminal (meth) acrylated carboxyl group-containing urethane resin. (7) reacting (meth)acrylic acid on a polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrogen in the hydroxyl group present in the side chain A photosensitive carboxyl group-containing resin obtained by addition of a 2-base acid anhydride such as phthalic anhydride. (8) reacting (meth)acrylic acid on a polyfunctional epoxy resin in which a hydroxyl group of a bifunctional (solid) epoxy resin is further epoxidized by epichlorohydrin, and is formed on the generated hydroxyl group A photosensitive carboxyl group-containing resin formed by addition of a two-base acid anhydride. Ti. SJi. -11 - 201105720 (9) The dicarboxylic acid is reacted on a bifunctional oxetane resin as described later, and a 2-base acid anhydride is added to the produced first-order hydroxyl group. A carboxyl resin-containing polyester resin. (10) Further, one of the molecules of the above-mentioned (1) to (9) has a ring of a molecule such as a glycidyl (meth) acrylate or an α-methylepoxypropyl (meth) acrylate. A photosensitive carboxyl group-containing resin obtained by adding an oxy group to a compound of one or more (meth) acrylonitrile groups. Among these carboxyl group-containing resins, preferred are (X) a carboxyl group-containing polyurethane resin, particularly an isocyanate group of an isocyanate group-containing component (diisocyanate) of the urethane resin. The polyfunctional epoxy resin used for the direct bonding to the benzene ring and the synthesis of the aforementioned resin has a bisphenol fluorene structure, a bisphenol F structure, a bisphenol structure, a biphenol aldehyde structure, and a bisxylenol structure. In particular, in the case of a compound having a biphenyl aldehyde structure and a hydride thereof, it is preferred because of low warpage and flexural resistance. Further, on the other hand, the modified product of the above (2), (3), (4), (5), (6) and the above (10) has a urethane in the main chain. Bonding, better for warping. Further, since the resin other than (1), (2) and (9) has a photosensitive group in the molecule, it is preferable because it has high photoreactivity. Further, in the present specification, the term "(meth)acrylate" collectively referred to as acrylate, methacrylate, and the like, is similar in other similar expressions. The carboxyl group-containing resin (A) is a crosslinking point at the time of thermal curing because it has a large number of free carboxyl groups in the side chain of the main polymer. Further, when it is a photocurable resin composition, it can be developed by a dilute aqueous alkali solution. Further, the acid value of the carboxyl group-containing resin (A) is preferably in the range of 30 to 200 mgKOH/g, more preferably 40 to 200 mgKOH/g, particularly preferably in the range of 45 to 120 mgKOH/g. From the viewpoint of alkali developability, if the acid value of the carboxyl group-containing resin is less than 30 mgKOH/g, alkali imaging is difficult, and if it exceeds 200 mgKOH/g, the exposure portion is dissolved by the developing solution. In the case of progress, the line width must be thinner than necessary, and the exposed portion and the unexposed portion may be dissolved and peeled off by the developing liquid without distinction, which may make the normal photoresist pattern drawing difficult. Further, although the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, it is usually in the range of 2,000 to 150,000, more preferably 5,000 to 10,000,000. When the weight average molecular weight is less than 2,000, the tack-removing property is poor, and the moisture resistance of the coating film after exposure is not good, and film peeling occurs at the time of development, and the resolution is greatly weakened. On the other hand, if the weight average molecular weight exceeds 1,500,000, the developability is remarkably deteriorated, and the storage stability is also poor. The amount of the carboxyl group-containing resin (A) is from 5 to 60% by mass, preferably from 1 to 60% by mass, more preferably from 20 to 60% by mass, particularly preferably from 3 to 10% by weight of the total composition. 50% by mass. When the amount is less than the above range, the film strength may be lowered. On the other hand, when it is more than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered.

I $ I aluminum hydroxide (B), which can be used directly by the market. For example, there are HIGILITE series, HW, H21, H31, H32, H42M, H4 3M, etc. manufactured by Showa Denko. In addition, the fine particle size of the aluminum hydroxide is effective in the folding endurance, and it is selected by a bead mill or the like in advance with a solvent or a resin, and is filtered by a sieve or the like. - 201105720 Other than 3 μιη or more is more preferable, and it is preferable from the viewpoint of the flame retardancy and flexibility of the hardened film obtained therefrom. The amount of the aluminum hydroxide (B) to be blended is 100 parts by mass of the carboxyl group-containing resin (A). The range of ~200 parts by mass is preferably from 1 to 15 parts by mass, more preferably from 10 to 1 part by mass. As the true spherical cerium oxide (C), commercially available true spherical cerium oxide having an average particle diameter of 0.25 μm, 0·5 μm, 1 μm, 1.5 μm, 2 μm, 3 μm, and 5 μm may be used as it is. In the case of commercial products, the company has a series of ADMATECHS SO series. Further, for the composition in which the true spherical cerium oxide is used, the decane coupling agent or the like may be directly used, but the solvent 'decane coupling agent and the true spherical cerium oxide may be used in advance as a bead mill or the like. After the surface treatment, the decane coupling agent is dispersed to uniformly treat the surface of the ceria, and further, it is preferred to filter particles having a particle size of 5 μm or more by sieving or the like, from the viewpoint of flexibility. The amount of the spheroidal cerium oxide (C) is preferably in the range of 1 to 200 parts by mass, preferably 1 to 150 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (Α). Good for 5 to 100 parts by mass. The composition of the present invention is composed of a thermosetting resin composition, and the thermosetting component (D) used for the purpose of improving the properties such as heat resistance and insulation reliability can be used in all cases. a compound having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group) in a molecule in which a carboxyl group of a resin of a carboxyl group is reacted, but a bifunctional or higher compound thereof The epoxy resin is preferred in terms of heat resistance and gold plating resistance, and in particular, an epoxy resin having a biphenyl aldehyde skeleton is heat-resistant and plated.

-14- 201105720 Gold resistance and flame retardancy are improved and better. In the case of the epoxy resin having a biphenyl aldehyde skeleton, for example, 1^(:-30001^, >1 (:-3000 'NC-3000H, NC-3100, etc.) manufactured by Sakamoto Chemical Co., Ltd. In the thermosetting resin composition of the present invention, a thermosetting component having two or more cyclic (thio)ether groups in a molecule of a thermosetting component may be used, and two or more members of the molecule have two or more members, three or four or five members. The compound having one or two kinds of the cyclic ether group or the cyclic thioether group of the ring may, for example, be a compound having two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1). a compound having two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, In the case of the above-mentioned polyfunctional epoxy compound (D-1), for example, jER828, jER834, jER1001, jER1004, manufactured by Japan Epoxy Resin Co., Ltd., and DIC Corporation EPICLON840, EPICLON8 5 0, EPICLON 1 050, EPICLON205 5, EPOTOHTO YD-0 by Dongdu Chemical Co., Ltd. 1 1 , YD-013 'YD-1 27, YD-1 28, D. E. R. 317, D. E. R. 331, D. E. R. 6 6 1 , D. E.R.664, ARALDITE6071, ARALDITE6084, ARALDITEGY250, ARALDITEGY260 from Ciba Specialty Chemicals, Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, AER 330 manufactured by Asahi Kasei Kogyo Co., Ltd. AER 331, AER 661, A. E. R. 664, etc. (all are trade names) 1 Si -15- 201105720 Bisphenol A type epoxy resin; JER YL9 03 made by Japan Epoxy Co., Ltd., DIC company EPICLON 152, EPICLON 165, EPOTOHTOYDB-400, YDB-500, manufactured by Tohto Kasei Co., Ltd., DER 542 manufactured by Dow Chemical Co., Ltd., ARALDITE 8011 manufactured by Ciba Specialty Chemicals Co., Ltd. - Sumiepoxy ESB-400 & Co., Ltd. manufactured by Sumitomo Chemical Industries Co., Ltd. ESB-700, Asahi Kasei AER 711, AER 714, etc. (both trade names) brominated epoxy resin manufactured by Industrial Co., Ltd.; jER152' jER 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN 431, DEN 438, manufactured by Dow Chemical Co., Ltd. EPICLONN-73 0, EPICLONN-770, E PIC L Ο NN - 8 6 5, EPOTOHTOYDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., ARALDITEECN 1 23 5, ARALDITEECN1273, ARALDITEECN1299, ARALDITEXPY3, manufactured by Ciba Specia 11y Chemicals 07. EPPN-201, EOCN-1 025 ' produced by Nippon Kasei Co., Ltd. EOCN- 1 020, EOCN-104S, RE-3 06, Sumiepoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, Ltd., manufactured by Asahi Kasei Co., Ltd. AER ECN-235, ECN-299, etc. (all are brand names) of novolac type epoxy resin; EPICLON 8 3 0 made by DIC Corporation, j ER 8 0 7 made by Japan Epoxy Resin Co., Ltd., manufactured by Dongdu Chemical Co., Ltd. EPOTOHTOYDF-170, YDF-175, YDF-2004, ARALDITEXPY306 (all are trade names) bisphenol F-type epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd.; EPOTOHTOST-2004, ST-2007, ST- manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A epoxy resin such as 3000 (trade name); jER604, manufactured by Nippon Epoxy Co., Ltd., -16-201105720 ΕΡΟΤ〇ΗΤΟΥΗ-434 manufactured by Toho Chemical Co., Ltd., AR manufactured by Ciba Specialty Chemicals Co., Ltd. ALDITEMY720, Sumi epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxy propylamine epoxy resin; and under the ARALDITECY-350 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. Hydantoin type epoxy resin; grease of AR ALD ITEC Y 1 75, CY 179, etc. (all trade names) manufactured by DAICEL Chemical Industry Co., Ltd., CELLOXIDE 2021, C ib a S pe ce al ty C h em ic al s Ring epoxy resin; YL·933 manufactured by Japan Epoxy Resin Co., Ltd., TEN, EPPN-501 'EPPN-502 manufactured by Dow Chemical Co., Ltd. (all are trade names), trihydroxyphenylmethane type epoxy resin; Japan Ethyl phthalate or bisphenol epoxy resin such as 丫1-6056, 丫--4 000, YL-612 1 (both trade names) manufactured by Epoxy Resin Co., Ltd. or a mixture of such; Ep S-200 manufactured by the company, EPX-3 0 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.; jER157S manufactured by Japan Epoxy Resin Co., Ltd. Bisphenol A novolac type epoxy resin (trade name); day JER YL-931 manufactured by Epoxy Resin Co., Ltd., ARALDITE 1 63 manufactured by Ciba Specialty Chemicals Co., Ltd. (all trade names), tetrahydroxyphenylethane type epoxy resin; ARALDITEPT 810 manufactured by Ciba Specialty Chemicals Co., Ltd., Nissan Chemical Industry Co., Ltd. Heterocyclic epoxy resin such as TEPIC (both trade names); diglycidyl phthalate resin such as BLEMMERDGT manufactured by Nippon Oil Co., Ltd.; tetramethyl propyl acrylate of ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Tetraglycidyl xylenoylethane acetonitrile resin; New Japan -17- 201105720 ESN-190, ESN-360 manufactured by Iron Chemical Co., Ltd. HP-4032, EXA-4750, EXA- manufactured by DIC Corporation Naphthyl epoxy resin such as 4700; epoxy resin having dicyclopentadiene skeleton such as HP-72〇0 and HP-7200H manufactured by DIC Corporation; CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Oxypropyl methacrylate copolymerized epoxy resin: copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene rubber derived (eg DABIL Chemical Industry PB-3600) Etc.), CTBN-modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more. In the above polyfunctional oxetane compound (D-2), in addition to bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxo) Heterocyclic butyl methoxy) methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3) -oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate '(3-ethyl-3-oxetanyl)methacrylate , (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or such oligomers or Examples of polyfunctional oxetane other than copolymers include oxetane and novolak resins, poly(P-hydroxystyrene), Cardo-type, and calixarene (calixarene). An etherified product derived from a resin having a base such as a caliperresorcinarene or a silsesquioxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned. -18-201105720 The epoxidized resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A-type cyclic sulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the like. Further, an epoxy group which substitutes an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom may be used in the same synthesis method. The amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably a ring (thio)ether group of 0.6 equivalent to 1 part of the carboxyl group of the carboxyl group-containing resin. 2. 5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the carboxyl group remains on the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like may occur. Lower, so it is not good. On the other hand, when it exceeds 2.5 equivalents, a low molecular weight cyclic (thio)ether group remains on the dried coating film, so that the strength of the coating film or the like is lowered, which is not preferable. The curable resin composition of the present invention has a thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule, in order to further improve heat resistance and insulation reliability of the cured coating film. In addition, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, an amine resin such as a melamine resin, a melamine derivative, or a benzoguanamine resin, a cyclic carbonate compound, or a double horse may be used. A known thermosetting resin such as an imine, an oxazine compound, an oxazoline compound, or a carbodiimide resin. In the case of a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound or one molecule, -19-201105720 A compound having two or more blocked isocyanate groups, that is, a blocked isocyanate compound or the like. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, and naphthalene-1,5- Diisocyanate, fluorene-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolyl dimer. Specific examples of the aliphatic polyisocyanate include tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl methyl double. (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, an adduct, a biuret, and an isocyanurate body β of the above-mentioned isocyanate compound may be mentioned, and the blocked isocyanate group contained in the above-mentioned blocked isocyanate compound may be mentioned. It is protected by the reaction of an isocyanate group and a block agent to form a temporarily inactive group. Upon heating to a predetermined temperature, the blocker dissociates to form an isocyanate group. In the case of the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent can be used. Examples of the isocyanate compound which can be reacted with the block agent include an isocyanurate type, a biuret type, and an adduct type. As the isocyanate compound, for example, an aromatic polyisocyanate, a fat -20-201105720 aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above. Examples of the isocyanate block agent include phenol-based block agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroguanamine, and γ-butane a guanamine-based blocker such as guanamine or β-propionalamine; an active methyl-blocking agent such as ethyl acetate or ethyl acetonide; 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 Alcohol blockers such as methyl ester, butyl glycolate, dipropyl copper alcohol, methyl lactate and ethyl lactate: formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime An oxime blocker such as bis-indenyl hydrazine or cyclohexane hydrazine: butyl thiol, hexyl thiol, t-butyl thiol, thiophenol, methyl thiophenol, ethyl thiophenol, etc. a thiol-based block agent; an amide-based blocker such as decylamine or benzamide; a quinone imide blocker such as succinimide succinate or succinimide; Aniline, butylamine, two Amine group of the amine blocking agent: imidazole, 2-ethylimidazole, etc. imidazole-based blocking agent; methylimine stretch and stretch propylene imine imine block, etc., and the like. The blocked isocyanate compound may be commercially available, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1 265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-21 17 ,

Desmosome 2170, Desmosome 2265 (above Sumitomo Bayer Carbamate Company, trade name), CORONATE 2512, -21 - 201105720

CORONATE 2513, CORONATE 2520 (above, manufactured by Japan Polyurethane Industrial Co., Ltd., trade name), 8-830, 8-8 15, 8-846, 8-870, B-874, B-882 (Mitsui Takeda Chemical company, trade name), TPA-B80E, 1 7B-60PX, E4 0 2 - B 8 0 T (manufactured by ASA ΗI KASEI CHEMICALS, trade name). Further, 31101 丨 <11^81^3 175 and BL-4265 are obtained by using methyl ethyl hydrazine as a block agent. The compound having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used alone or in combination of two or more. The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 1 part by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (A). It is suitable for a ratio of 2 to 70 parts by mass. When the amount of the above combination is less than 1 part by mass, sufficient coating film toughness cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability of the composition may be lowered, which is not preferable. Further, examples of the other thermosetting component include a melamine derivative and a benzoguanamine derivative. For example, there are a methylol melamine compound, a hydroxymethyl benzoguanamine compound, a methylol acetylene urea compound, and a methylol urea compound. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated acetylene urea compound, and an alkoxymethylated urea compound may each have a methylol group The melamine compound, the hydroxymethyl benzoguanamine compound, the methylol acetylene urea compound, and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxymethyl-22-201105720 group, a propoxymethyl group or a butoxymethyl group. In particular, it is preferred to use a melamine derivative having a concentration of 0.2% or less of a fumarin concentration excellent in the human body or the environment. For such commercial products, for example, Cymel 3 00, the same 301, the same 303, the same 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 238, the same 1141, the same 272, the same 202 , with the same 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above is Mitsui Cyanamid (share) system), NIKALAC Mx-750, the same Mx-032, the same Mx-270, the same Mx- 280, the same Mx-290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw-30, the same Mw-30HM, the same Mw-390 'the same Mw- 100LM, same as Mw-750LM (above is Sanwa Chemical (share) system). The above thermosetting component may be used alone or in combination of two or more. When the thermosetting component (D) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1- Imidazole derivatives such as cyanoethyl-2-phenylimidazole, cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-( Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzene An amine compound such as a methylamine, a ruthenium compound such as diammonium adipate or a ruthenium sebacate; a phosphorus compound such as triphenylphosphine; and a commercially available product, for example, manufactured by Shikoku Kasei Co., Ltd. 2MZ-A, 2MZ-0K, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds), U-CAT (registered by -23-201105720) 3503N, U-CAT3502T manufactured by SAN-APRO Co., Ltd. A trade name of a blocked isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, and U-CAT5002 (all of which are bicyclic hydrazine compounds and salts thereof). These are not particularly limited, and may be used alone as a thermosetting catalyst for an epoxy resin or an oxetane compound, or for promoting an epoxy group and/or an oxetanyl group and a carboxyl group. Or use two or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4- can be used. Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Iso-cyanuric acid adduct, 2,4-diamino-6-methylpropene oxime An S-triazine derivative such as an oxyethyl-S-triazine, an isomeric cyanuric acid addition product, or the like, and a compound for imparting such a adhesion imparting agent to the above-mentioned thermosetting catalyst It is better. The amount of the thermosetting catalyst is preferably in a ratio of a normal amount, for example, 100 parts by mass of the carboxyl group-containing resin (A), preferably 0.1 to 20 parts by mass, more preferably 〇.5. ~15.0 parts by mass. The curable resin composition of the present invention preferably contains a phosphorus-containing compound (E). In the case of a phosphorus-containing compound, it may be a conventionally known organic phosphorus-based flame retardant, which is preferably a phosphate ester and a condensed phosphate ester, a cyclic phosphine oxide compound, an azophosphonium oligomer, a phosphonate or the following. a compound of the formula (I). -24 - 201105720

In the formula, R1, R2 and R3 each independently represent a substituent other than a halogen atom. The commercially available product of the above-mentioned general formula (I) is HCA, SANKO-220 'M-ESTER, HCA-HQ (all are trade names of Sanguang). The phosphorus-containing compound (E) which is particularly preferably used in the invention may, for example, be (1) having an acrylate group or (2) having a phenolic hydroxyl group, (3) an oligomer or a polymer, ( 4) an azophosphorus oligomer and (5) a phosphonate as a reactive group. (1) A phosphorus-containing compound having an acrylate group. The acetophenone-containing acetoacetate has a dish element and is in a molecule. A compound having two or more (meth) acrylates is preferable, and specifically, a compound in which R1 and R2 in the above general formula (1) are a hydrogen atom and R3 is an acrylate derivative is generally used. It is synthesized by an addition reaction of 9,10-dihydro-9-oxa-1-phosphaphenanthene-yttrium oxide with a conventionally known polyfunctional acrylate monomer, Mai-25-201105720. Examples of the above-mentioned conventionally known acrylate monomer include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol 'polyethylene glycol, and propylene glycol; hexane diol and trimethylol Polyols such as propane, pentaerythritol, dipentaerythritol, isocyanurate or the like, or such ethylene oxide adducts, propylene oxide adducts or caprolactone adducts, etc. Valence acrylates: phenoxy acrylate, bisphenol A diacrylate, and phenolic ethylene oxide adducts such as phenols or polyvalent acrylates such as propylene oxide adducts; and the above polyols Urethane acrylates, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, trisepoxypropyl isocyanurate A polyvalent acrylate of a glycidyl ether such as an isocyanurate: and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. (2) Phosphorus-containing compound having a phenolic hydroxyl group The phosphorus-containing compound having a phenolic hydroxyl group is highly hydrophobic and heat-resistant, and the electrical properties due to hydrolysis are not lowered, and the solder has high heat resistance. Further, a preferred combination is obtained by introducing an epoxy resin having a biphenyl skeleton or another epoxy resin as the component (D) into the network by reacting with the epoxy resin, so that it can be bleed out after hardening. The advantages. In the case of commercial products, there are HCA-HQ manufactured by Sanguang Co., Ltd. (3) Oligomers or polymers Phosphorus compounds of oligomers or polymers have less reduction in flexibility due to the influence of alkyl chains, and can be hardened after being hardened due to large molecular weight.

-26- 201105720 (bleed out) advantages. In the case of commercial products, there is a three-light (share) system 1 Ester-HP 'Toyobo Co., Ltd.'s phosphorus-containing VYLON 337. (4) In terms of the azophosphorus oligomer azophosphorus oligomer, the phenoxy phosphine nitrogen compound is effective, and has a substituted or unsubstituted phenoxy azophosphorus oligomer or a triad, 4 Rings of 5 parts and 5 parts, and liquid or solid powders are applicable. For commercial products, there are FP-100, FP-3 00, FP-3 90, etc. manufactured by Fushimi Pharmaceutical Co., Ltd. Among them, a phenoxy phosphatidyl oligo group substituted with a polar group such as an alkyl group or a hydroxy group or a cyano group has high solubility in a carboxyl group-containing resin, and does not recrystallize even if it is added in a large amount. good. (5) Phosphonate By using a phosphonate, the flame retardancy can be improved without impairing the softness of the hardened coating film. Further, by using a phosphonate having excellent heat resistance, it is possible to suppress bleed out of the flame retardant during hot pressing at the time of mounting. For the commercial products, EXOLIT OP 930, EXOLIT OP 93 5, etc., manufactured by Clariant Co., Ltd., may be mentioned. The amount of the phosphorus-containing compound (E) of the flame retardant is preferably in the range of from 〇 to 200 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A), particularly preferably from 100 parts by mass to 100 parts by mass. . If it is more closely matched with this, the bending characteristics and the like of the obtained hardened film may be deteriorated. In the photopolymerization initiator (F) constituting the photocurable resin composition of the present invention, photopolymerization initiation of an oxime ester photopolymerization initiator having an oxime ester group and α-aminoacetophenone photopolymerization can be used. One or more kinds of photopolymerization initiators selected from the group consisting of a reagent and a mercaptophosphine oxide photopolymerization initiator. -27- 201105720 The oxime ester photopolymerization initiator is Ciba, which is a commercial product.

CGI-325, IRUGACURE OXEOl, IRUGACURE OXE02 manufactured by Specialty Chemicals, N-1919 manufactured by ADEKA, ADEKA ARKLS NCI-831, etc. Further, a photopolymerization initiator having two oxime ester groups in the molecule can be used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula can be mentioned. [Chemical 2]

(wherein, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having a carbon number of 1 to 8 'phenyl group (an alkyl group having a carbon number of 1 to 17 and an alkoxy group having a carbon number of 1 to 8) a group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and a naphthyl group (an alkyl group having a carbon number of 1 to 17 carbon number of 1 to 8) An oxy group, an amine group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, and Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 ～8 alkoxy'halo, phenyl, phenyl (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) a substituted alkylamino or dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms) Alkenylamino or dialkylamino group substituted), mercapto, pyr-28-201105720 pyridine, benzofuranyl, benzothienyl, Ar represents alkylene with a carbon number of 1 to 10, ethylene Base, phenylene, biphenyl, exopyridyl, naphthyl, thiophene, thiophene (thienylene), furfuryl, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, η is an integer of 0 or 1. In particular In the above formula, each of ruthenium and osmium is methyl or ethyl, Ζ is methyl or phenyl, η is 0, and Ar is phenyl, thiophene, thiophene or thienylene. Preferably, the α-aminoacetophenone photopolymerization initiator is specifically 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino. Acetone-1, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, anthracene, fluorene-dimethylaminoacetophenone, etc. Commercial products For example, IRUGACURE 907, IRUGACURE 369, IRUGACURE 3 79, etc., manufactured by Ciba Specialty Chemicals Co., Ltd., etc. The mercaptophosphine oxide photopolymerization initiator is specifically 2,4,6-trimethylbenzene. Mercapto diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2, 4,4-three A commercially available product, such as Lucirin TPO manufactured by BASF Corporation and IRUGACURE 819 manufactured by Ciba Specialty Chemicals Co., Ltd., etc. Among the above photopolymerization initiators, particularly preferred fluorenylphosphine oxidation The initiator of the system has the best light permeability from the viewpoint of photobleach performance and has an effect on flame retardancy. Moreover, the oxime ester-based initiator has a good efficiency of starting from -29 to 201105720, and a small amount has an effect on sensitivity improvement, so that the exhaust gas during the heat treatment after the formation of the photoresist film is less, and the film is warped. It is better to have a reduction in the curvature of the song. Especially good for both. The amount of the photopolymerization initiator (F) to be used is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the photopolymerization initiator (F) is less than 0.01 parts by mass, the photocurability on the copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the light absorption on the surface of the solder resist coating film of the photopolymerization initiator (F) becomes intense, and the deep hardenability is lowered, which is not preferable. Further, when it is an oxime ester-based photopolymerization initiator having a group represented by the above formula (Π), the amount of the carboxyl group-containing resin (A) is preferably 0.01 to 20 parts by mass. The mass fraction is more preferably in the range of 0.01 to 5 parts by mass. Other examples of the photopolymerization initiator, photoinitiator, and sensitizer which can be used in the photocurable resin composition of the present invention include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantate. A ketone compound, a ketal compound, a diphenyl ketone compound, an oxonone compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1 , 1_二-30- 201105720 Chloroacetophenone. Specific examples of the hydrazine compound include, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, and 1-chloroindole. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthene. Hey. Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Specific examples of the diphenyl ketone compound include diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyl diphenyl sulfide, and 4-benzene. Mercapto-4'-ethyldiphenyl sulfide '4-benzylidene- 4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminodiphenyl ketone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.). 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminodibenylhydrazine, 7-(ethylethenyl)-4-methyl-2H- a dialkylamino group-containing coumarin compound or 4-dimethylamino group, such as 1-benzo0-pyran-2-indole (7-(diethylamino)_4-methylcoumarin) Benzoic acid ethyl (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (Quantacure DMB manufactured by International Biosynthetics), 4-dimethylamino benzoic acid (η-butoxy) Ethyl (Quantacure BEA, manufactured by International Biosynthetics Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (KAYACURE -31 - 201105720 DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2 Ethylhexyl (Esolol 507, manufactured by van Dyk Co., Ltd.), 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.). Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, it is preferable to use a thioxanthone compound from the viewpoint of deep hardenability, and more preferably 2,4-dimethylthioxanthone or 2,4-diethylthioxanthone. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred. The amount of the thioxanthone compound to be used is preferably 20 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). If the compounding amount of the compound is too large, the thick film hardenability will be lowered, which is related to the cost of the product, which is not preferable. In the case of a tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, wherein a dialkylaminodiphenyl ketone compound is further contained, and a dialkylamine group having a maximum absorption wavelength of 3 50 to 41 Onm is preferred. The coumarin compound is particularly preferred. The dialkylaminodiphenyl ketone compound is preferably 4,4'-diethylaminodiphenyl ketone with low toxicity. • The dialkylamine containing a maximum absorption wavelength of 3 50 to 41 Onm Since the coumarin compound has a maximum absorption wavelength in the ultraviolet region, its coloring is small, and the colorless and transparent photosensitive composition can provide a color resist film which reflects the color of the coloring pigment itself by using a coloring pigment. Particularly, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm. The amount of the tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the above-mentioned carboxyl group-containing 32-201105720 resin (A). The ratio. When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. On the other hand, when it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film is severe due to the tertiary amine compound, and the deep hardenability tends to decrease. In order to improve the sensitivity of the photocurable resin composition of the present invention, conventionally known N-phenylamino acetic acid, phenoxyacetic acid, thiophenoxyacetic acid, thiol thiazole or the like can be used. Chain transfer agent. Specific examples of the chain transfer agent include chain transfer of a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof. a chain transfer agent having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof: 1-butane sulfur Alcohol, butyl-3-mercaptopropionate 'methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenesulfide Alcohol, dodecyl mercaptan, propane thiol, butane thiol, heptane thiol, 1-octane thiol, cycloheptane thiol, cyclohexane thiol, thio glycerol, 4, 4 - thiobisbenthiol and the like. Further, as the heterocyclic compound having a mercapto group acting as a chain transfer agent, for example, mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4-methyl group 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butylidene, N- Methoxy-2-mercapto-4-butylidene, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-indole-33- 201105720 base-4 - Butyrolactam, N-ethyl-2-mercapto-4-butylidene, Ν·(2-methoxy)ethyl-2-mercapto-4· Buteneamine, Ν-( 2-ethoxy)ethyl-2-mercapto-4-butylidene, 2-mercapto-5-valerolactone, 2-indolyl-5-pentalinamide, guanidine-methyl-2- Mercapto-5-valeroinamide, Ν-ethyl-2-mercapto-5-pentalinamide, Ν-(2-methoxy)ethyl-2-mercapto-5-pentalamine, Ν-(2-ethoxy)ethyl-2-mercapto-5-pentalinamide and 2-mercapto-6-caprolactam and the like. In particular, in the case of a heterocyclic compound having a mercapto group as a chain transfer agent without impairing the developability of the photocurable resin composition, mercaptobenzothiazole and 3-mercapto-4-methyl-4-indole are used. Preferably, 1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1Η-tetrazole. These chain transfer agents may be used alone or in combination of two or more. These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curing property tends to be lowered by such light absorption. The photopolymerizable monomer (G) used in the photocurable resin composition of the present invention is photocured by irradiation with an active energy ray, and the photocurable resin composition of the present invention is insoluble. In an aqueous alkali solution, or to help insoluble. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexane diol, trimethylolpropane, pentaerythritol, and a polyhydric alcohol such as pentaerythritol, isocyanatoic acid or the like, or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct such as -34-201105720; a polyvalent acrylate such as an oxy acrylate, a bisphenol A diacrylate, or a phenolic ethylene oxide adduct or a propylene oxide adduct; glycerol diepoxypropyl ether, C a polyvalent acrylate of a glycidyl ether such as triol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, trisethoxypropyl isocyanurate or the like; and melamine An acrylate, and/or each methacrylate corresponding to the above acrylate. Further, an epoxy acrylate resin obtained by reacting acrylic acid on a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a pentaerythritol three on the hydroxyl group of the epoxy acrylate resin may be mentioned. An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate such as acrylate with a halfurethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve photocurability without lowering the dryness of the finger touch. The amount of the photopolymerizable monomer (G) having two or more ethylenically unsaturated groups in the molecule is 1 part by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). More preferably, it is a ratio of 5 to 70 parts by mass. When the amount of the collocation is less than 5 parts by mass, the photocurability is lowered, and it is difficult to form a pattern by alkali imaging after irradiation with an active energy ray. On the other hand, when it exceeds 1 part by mass, the solubility in the aqueous alkali solution is lowered to make the coating film brittle, which is not preferable. The curable resin composition of the present invention can be blended with a coloring agent (H). As the coloring agent (H), a conventionally known -35-201105720 coloring agent such as red, blue, green or yellow may be used, and any of a pigment, a dye and a coloring matter may be used. Specifically, the number of the color cable (C.I.: The Society of Dyers and Colourists) as described below can be cited. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferred that halogen is not contained. Red coloring agent: Red coloring agent is monoazo, diazo, monoazo, benzimidazolone, anthracene, diketopyrrolopyrrole, condensed azo, hydrazine The quinone, the quinacridone system, etc., specifically, the following are mentioned. Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9 , 12 , 14 , 15, 16, 17, 21, 22 > 23, 3 1, 32, 112, 114, 146 , 147, 151, 170, 184 i 1 8 7, 18 8, 193, 2 10 , 245 , 253 , 258 > 266, 267 , 268 , 269 〇 Diazo : Pigment Red 37 , 3 8 , 4 1 ° Monoazo lake system: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2 > 50:1, 52:1, 52:2, 53:1, 53:2 > 57:1, 58:4, 63:1, 63:2, 64:1, 68. Benzymidone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, P i gm ent Re d 2 0 8 o JE series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 o 201105720 diketone-based singularity: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272 - condensed azo system: Pigment R ed 2 2 0, Pigment R ed 1 4 4, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 22 1 ' Pigment Red 242. Green onion: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 5 2 'S ο 1 vent Red 2 07 o Quinacridone: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209. Blue colorant: For blue colorants, there are anthracyclines, anthraquinones, and pigments are classified as Pigment compounds, specifically: Pigment Blue 15 and Pigment Blue 15: 1 , Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4 ' Pigment Blue 15:6, Pigment Blue 16 ' P i gm en t B lu e 6 0 ° i S 1 Dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. are used. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used. -37- 201105720 Green colorant: For green colorants, there are also anthracyclines, lanthanides, and lanthanides. In particular, ment' can use Pigment Green 7, Pigment

Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. In addition to the above, an anthraquinone compound substituted with or without a metal may also be used. Yellow coloring agent: The yellow coloring agent is a monoazo type, a diazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, etc., Specifically, the following are mentioned Listed. Scallions: S ο 1 v e n t Y e 11 〇 w 1 63, Pigment Yellow 24' Pigment Yellow 108, Pigment Yellow 193, Pigment

Yellow 147, Pigment Yellow 199, Pigment Yellow 202. Isoindole ketones: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139 ' Pigment Yellow 179 ' Pigment Yellow 185. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment

Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzimidone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154 ' Pigment Yellow 156 ' Pigment Yellow 175, Pigment Yellow 181. Monoazo system: Pigment Yellow 1, 2, 3' 4' 5' 6' 9 , 10 , 12 , 61 , 62 * 62:1 , 65 , 73 , 74 ,

-38- 201105720 /5 ’ 97 , 100 , 104 , 105 , 111 , 116 « 167 , 1 68 , 169 , 182 , 183 . Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 5 5 63 8 1 '83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198. Others For the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown or black may be added. Specifically, it can be exemplified as Pigment Violet 19, 23, 29, 32, 3, 38, 42, Solvent Violet 13, 36, CI color orange 1, CI color orange 5, d color material orange 13 Ci color orange 14, CI color orange 16, CI color orange 17, CI color orange 24, CI color orange 34, CI color orange 36, CI color orange 38, CI color orange 40, CI color orange 43, CI color orange 46, CI color orange 49, CI color orange 51, CI color orange 61, C.I_ color orange 63, CI color orange 64, CI color orange 71, CI color orange 73, CI · color brown 23, CI color brown 25, CI color black 1, CI color black 7 and so on. The mixing ratio of the above-mentioned coloring agent (H) is not particularly limited, and it is preferably 0 to 1 part by mass, particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin (A) containing the residue. The ratio is sufficient. In order to enhance the physical strength and the like of the coating film, the curable resin composition of the present invention can be blended with the material as needed. As such a material, conventionally known inorganic or organic materials can be used. In addition to the aluminum hydroxide and the true spherical cerium oxide previously exemplified, barium sulfate and sulphuric acid S::-39- can also be used. 201105720 矽, talc, magnesite, magnesium hydroxide 'bo emit e', alumina, titanium oxide, etc., which can be used alone or in combination of two or more. The amount of the above-mentioned materials is preferably 300 parts by mass or less, more preferably 〇1 to 300 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A), which is particularly preferably 〇·1 to 150. Parts by mass. When the amount of the mash is more than 300 parts by mass, the viscosity of the curable resin composition becomes high, the printability is lowered, and the cured product becomes brittle. In the curable resin composition of the present invention, a conventionally known binder polymer can be used for the purpose of improving flexibility and dryness. The binder polymer is preferably a cellulose-based, polyester-based or phenoxy resin-based polymer. Examples of the cellulose-based polymer include Cellulose Acetate Butyrate (CAB) and Cellulose Acetate Propionate (CAP) series manufactured by Eastman Co., Ltd., and polyester-based polymers, preferably VYLON series manufactured by Toyobo Co., Ltd., and phenoxy resin system. In terms of polymer, bisphenol A, bisphenol F and phenoxy resins of such hydrides are preferred. The amount of the binder polymer to be added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, even more preferably 5 to 30 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the binder polymer is more than 50 parts by mass, the alkalinity of the curable resin composition is poor, and the start time of development can be shortened. In the curable resin composition of the present invention, in order to enhance the interlayer As the adhesion, or the adhesion between the photosensitive resin layer and the substrate, an adhesion promoter can be used. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazide.

-40- 201105720 azole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-mercaptomethyl-thiazolidine-2-thiol, 2- Sulfhydryl-5-methylthio-thiadiazepine, triterpene, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, sane coupling agent, and the like. In general, when a large amount of a polymer material starts to oxidize, that is, a chain oxidative degradation occurs immediately, and the function of the polymer material is lowered, the curable resin composition of the present invention can be added (i) in order to prevent oxidation. a radical scavenger which can invalidate generated radicals and/or (2) an antioxidant which decomposes the generated peroxide into a harmless substance and does not generate a new radical peroxide decomposing agent . The antioxidant acting as a radical scavenger, and specific examples thereof include hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, and hydroquinone. Monomethyl ether, 2,6-di-t-butyl-P-cresol, 2,2-methyl-bis(4-methyl-6-t-butylphenol), l,l,3 - ginseng (2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t- Butyl-4-hydroxybenzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-3-triazine-2,4, a benzoquinone compound such as phenol, methyl benzoquinone or benzoquinone such as 6-(111, 311, 511) triketone, bis(2,2,6,6-tetramethyl-4-piperidine) An amine compound such as a sebacate or a phenothiazine. The radical scavenger may be commercially available, and may, for example, be ADK STAB AO-30, ADK STAB AO-3 30, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA- 67, ADK STAB LA-68, ADK STAB LA-87 (above is manufactured by Asahi Kasei Co., Ltd.) 'IRGANOXIOIO, IRGANOX1 035,, -41 - 201105720 IRGANOX1 076, IRGANOX1 135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TI such as TINUVIN 152, TINUVIN 292, and TINUVIN 5100 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) and the like are antioxidants of a peroxide decomposer, and specific examples of the compound include triphenyl phosphite. A sulfur compound such as a phosphorus compound, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate or distearyl 3,3'-thiodipropionate. The peroxide decomposing agent may be, for example, ADK STAB TPP (manufactured by Asahi Kasei Co., Ltd., trade name), Mark AO-412S (made by Adeka ARGUS Chemical Co., Ltd., trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., Product name). These antioxidants may be used alone or in combination of two or more. In general, since the polymer material absorbs light and is decomposed and deteriorated, the curable resin composition of the present invention can be used in addition to the above-mentioned antioxidant, in addition to the above-mentioned antioxidant. . Examples of the ultraviolet absorber include a diphenyl ketone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamic acid ester derivative, and an ortho-amine benzoate. An acid ester derivative, a benzhydrylmethane derivative or the like. Specific examples of the diphenyl ketone derivative include 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-n-octyloxydiphenyl ketone, and 2,2'-dihydroxy- 4-methoxybenzophenone and 2,4-dihydroxydiphenyl-42-201105720 ketone and the like. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, and 2,4-di-t-. Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2-(2-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5,-methylphenyl group. Benzotriazole, 2-(2,-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-3,, 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2·(2'-hydroxy- 3,5,-di-t-pentylphenyl)benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyltriazine and diethylhexyloxyphenol methoxyphenyltriazine. The ultraviolet absorber may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (the above is manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) and the like. The above-mentioned ultraviolet ray absorbing agent may be used singly or in combination of two or more kinds thereof, and it is intended to stabilize the molded article obtained from the curable resin composition of the present invention by the use of the above-mentioned antioxidant. Further, in the curable resin composition of the present invention, an organic solvent can be used for the adjustment of the synthesis or composition of the carboxyl group-containing resin (A) or the viscosity adjustment for coating on a substrate or a carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, di-43-201105720 alcohol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethoxyethanol, methyl ethoxyethanol, and butyl b. Oxyethanol, diethylene glycol ethyl ether, methyl diglycol ether, butyl diglycol ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl Glycol ethers such as ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate Esters such as alcohols; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum systems such as petroleum ether, petroleum light oil, hydrogenated petroleum light oil, and solvent light oil. Solvents, etc. Such an organic solvent may be used singly or in combination of two or more. The curable resin composition of the present invention may be blended with a conventionally known thermal polymerization inhibitor, fine powder of cerium oxide, organic clay, montmorillonite, or the like, and an anthrone-based "fluorine-based". A well-known and conventional additive such as a defoaming agent and/or a leveling agent such as a polymer, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, an antioxidant, and a rust preventive agent. The aforementioned thermal polymerization inhibiting agent can be used to prevent thermal polymerization or time-lapse polymerization of the above polymerizable compound. Examples of the thermal polymerization inhibiting agent include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butyl catechol, benzenetriol, and 2-hydroxydiphenyl. Ketone, 4-methoxy-2-hydroxydiphenyl ketone, copper chloride (CuCl), phenothiazine, tetrachlorophenyl hydrazine, naphthylamine, β-naphthol, 2,6-di-t-butyl 4-methylphenol, 2,2'-methyl bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, trinitrobenzene-44-201105720 Phenol, 4-toluidine, methyl blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and A1 chelate. The curable resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer formed of the curable resin composition formed on the carrier film. In the case of dry film formation, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to a suitable viscosity, and is used as a comma coater or a blade coater. , a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll A coater, a gravure coater, and a spray coater are coated on the carrier film to have a uniform thickness, and are usually dried at a temperature of 50 to 130 ° C for 1 to 30 minutes to obtain a coating film. The coating film thickness is not particularly limited, but the film thickness after drying is generally 10 to 150 μm, and it is preferably selected in the range of 20 to 60 μm. For carrying the film, a plastic film is used, in which a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like is used. The plastic film is preferred. The thickness of the carrier film is not particularly limited, and generally, it can be appropriately selected from the range of 1 〜 to 150 μm. After the film is formed on the carrier film, it is preferable to laminate a peelable coating film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. For the S S1 peelable coating film, for example, a polyethylene film '-45-201105720 PTFE film, a polypropylene film, a surface-treated paper, or the like can be used, and when the coated film is peeled off, if it is a film and a coated film, Then the force is less than the adhesion of the film and the carrier film. The curable resin composition of the present invention is adjusted to have a viscosity suitable for the coating method, for example, by a dip coating method, a cast coating method, a roll coating method, or a bar coating on a substrate. Coating by a method such as a method, a screen printing method, a curtain coating method, etc., and the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a debonding method. Coating film. In addition, when the composition is applied onto a carrier film, dried, and wound into a dry film as a film, the curable resin composition layer is brought into contact with the substrate by a laminator or the like. After the substrate is peeled off, the carrier film is peeled off to form a resin insulating layer. When it is a photocurable resin composition, it is then passed through a contact type (or non-contact mode) to transmit a patterned light mask. Alternatively, it may be exposed by an active energy ray or directly exposed by a laser direct exposure machine, and the unexposed portion may be developed with a dilute aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution). Form a photoresist pattern. When the composition further contains the thermosetting component (D), it is thermally cured by, for example, heating to a temperature of about 140 to 180 ° C, and has two or more cyclic ether groups and/or rings in the molecule. The thermosetting component (D) of the thioether group reacts with the carboxyl group of the carboxyl group-containing resin (A) to form heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical properties and the like. A hardened coating that excels in performance. Further, even if the thermosetting component (D) is not contained, by the heat treatment, the ethylenically unsaturated bond remaining in the unreacted state during the exposure is thermally polymerized, and the coating film is lifted. The characteristics can be heat treated (thermosetting) depending on the purpose and use. In terms of the above-mentioned substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth may be used. /Non-woven epoxy, glass cloth/paper epoxy, synthetic bismuth epoxy, fluorine, polyethylene, PPO, cyanate, etc. All grades (FR-4, etc.) copper-clad laminates, other polyimine Film 'PET film, glass substrate, ceramic substrate, wafer board, etc. The volatilization drying performed after applying the curable resin composition of the present invention may be a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (using a heat source having a method of heating air by means of steam, This can be carried out by means of a method in which the hot air in the dryer is in contact with each other and a method of blowing the support from the nozzle. In the case of a photocurable resin composition, the coating film obtained after coating and volatilizing the solvent is exposed (exposure by active energy rays) to expose the exposed portion (the portion irradiated by the active energy ray) )hardening. The above-mentioned exposure machine for active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in a range of 350 to 450 nm. A direct rendering device (eg, a direct laser imaging device that directly renders an image based on laser data from a computer) can be used. For the laser source of the direct drawing machine, if laser light having a maximum wavelength of 350 to 410 nm is used, it may be either a gas laser or a solid laser. The amount of exposure for image formation varies depending on the film thickness, etc., but is generally 20 to -47 to 201105720 8 Ο 0 m J / cm 2 , preferably in the range of 2 0 to 6 Ο 0 m J / cm 2 . The above-mentioned development method can be used for the dipping method, the rinsing method, the spraying method, the painting method, etc., and the potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate can be used as the developing liquid. An aqueous solution of an alkali such as sodium citrate, ammonia or an amine. [Examples] Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are all based on the quality standard without any particular limitation. Synthesis of the resin (A-1) corresponds to the resin of the carboxyl group-containing resin (5): In a reaction vessel of a thermometer and a capacitor, a polycarbonate diol derived from I,5-heptanediol and 1,6-hexanediol (made by ASAHI KASEI CH EM IC ALS), TJ5650J, Number average molecular weight 800) 2400g (3 moles), dimethyl propyl propionate 603g (4.5 moles) and 2-hydroxyethyl acrylate as a monohydroxy compound 23 8g (2.6 moles) ° Isophorone diisocyanate of polyisocyanate 1 8 87 g (8.5 m), stopped after heating to 60 ° C with stirring, and reheated when the temperature in the reaction vessel began to decrease, and continued stirring at 8 (TC) The absorption spectrum confirmed that the absorption spectrum of the isocyanate group (2 280 cm-i) disappeared and the reaction was completed. Diethylene glycol ethyl ether acetate was added to separate the solid content into 5 〇 mass%. The acid value of the solid content of the obtained carboxyl group-containing resin was - 48- 201105720 50mgKOH/g. (A-2) equivalent The photosensitive carboxyl group-containing resin of the carboxyl group-containing resin (7): a photosensitive carboxyl group-containing resin having a photosensitive group and a polyfunctional epoxy having a biphenyl aldehyde structure--ZCR-1601H manufactured by Nippon Kayaku Co., Ltd. The resin solution (solid content: 65%; resin acid value: 98 mgKOH/g) was A-2. Preparation of aluminum hydroxide slurry: 700 g of aluminum hydroxide (HIGILITE 42M manufactured by Showa Denko) was used as a solvent. Diethylene glycol diethyl ether acetate 280g, BYK-1 1 20 20g were mixed and stirred, and dispersed on a bead mill using 0.5 μηη zirconia beads. This was repeated 3 times and made through a 3 μm filter. Aluminum hydroxide slurry (Β-1). Preparation of cerium oxide slurry: 700 g of true spherical cerium oxide (S0-E2 manufactured by ADMATECHS Co., Ltd.) and diethylene glycol diethyl ether acetate as a solvent were mixed and stirred. 295 g of a vinyl decane coupling agent as a decane coupling agent was dispersed in a bead mill in the same manner as described above. This was repeated three times, and filtered through a 3 μm filter to prepare a cerium oxide slurry (C- 1) Similarly, true spherical cerium oxide (SO·C5 manufactured by ADMATECHS) 700 g was dispersed with the above-mentioned dioxin-comprising material R, and a ceria slurry (c-2) was prepared by a filter of 5 μm. Examples 1 to 9 and Comparative Examples 1 to 4 Resins of the above synthesis examples were used. The solution 'mixed with the various components shown in Table 1 -49-201105720 in the ratio (parts by mass) shown in Table 1, and after the preliminary mixing in the mixer, the '3 light sander (triple r〇n mill) was kneaded. , Modifying the solder resist curing resin composition. Here, the degree of dispersion of the obtained curable resin composition was evaluated by particle size measurement by a particle size analyzer manufactured by Erik Sen Co., Ltd., and was 15 μm or less.

-50- 201105720 [Table 1] Composition valence) Example Comparative Example 1 • 2 3 4 5 6 7 8 9 1 2 3 4 A component varnish, .. 115 115 115 115 115 115 115 115 180 115 115 115 115 Varnish 2·· 50 SO 50 50 50 50 50 50 50 50 50 50 B component Β*Γ* 70 70 70 100 70 70 70 70 70 140 100 C component c-ra 70 70 45 30 70 70 70 70 C-2· * 70 140 D component NC-3100·* 40 40 40 40 40 40 40 40 40 40 40 40 40 E component FP-390·* 40 30 30 30 60 30 30 10 30 30 30 60 30 Exolit OP 935*® 20 10 F component TPO° 10 10 10 10 10 10 10 10 10 61 10 G component DPCA60·* 20 20 20 20 10 10 10 10 20 20 20 20 HFA-6065P'· 50 50 50 50 50 SO 60 60 50 50 50 50 Phosphorus-containing 3 K polymerization initiator 1M() 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Non-containing dish eve poly-starting engraving · 11 0.8 0.5 heat-hardening touch I melamine 5 5 5 5 5 5 5 5 5 5 5 5 5 DHT-4A,, j 5 10 Dipropylene glycol monomethyl ether 5 fluorenone defoamer 3 3 3 3 3 3 3 .3 3 3 3 3 3 袢 13 13 1.1 1.1 1.1 UU 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 IRGANOX1010*'4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 TPA-B80E*18 5 5 5 Oryzanol varnish % 33 33 33 33 33 33 33 33 33 33 33 33 33 Mercaptobenzothiazole 0.5 0.S 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 : varnish Α · 1 (solid component 60%) varnish A-2 (solid content 65%) ·: Showa electrician (stock) aluminum paste '(share) ADMATECHS made spherical cerium oxide slurry, bismuth phenolic varnish type epoxy resin (share) made by Fuji Chemical Co., Ltd. Fushi Pharmaceutical Co., Ltd. contains flame retardant containing dish ··: 'Clarian Uapan Co., Ltd. 'Japan SiberHegner Co., Ltd. Phosphorus-containing photopolymerization initiator TPO ": Nipponization drug (K) made of dipentaerythritol lactone modified hexaacrylate": Showa polymer (share) phosphorus compound modified acrylic Ester (solid content 80%; propylene glycol monomethyl ether acetate 20%) • I»: 2-(ethylideneoxyiminomethyl) thioxanthene-9-one ·": (IS)ADEKA Photopolymerization starter ADEKA ARKLS NCI-831 .,*: Polygonistite compound of Concord Chemical Industry Co., Ltd. ·'': 0.3 parts of CIPigmentBlue 15:3 and C_I.PigmentyelIowl4 0.8 parts of 7 parts "": a free radical scavenger manufactured by Ciba Specialty Chemicals Co., Ltd., a block isocyanate compound manufactured by ASAHI KASEI CHEMICALS Co., Ltd. - CAB-553, manufactured by EASTMAN Co., Ltd. 0.4 (ethyl ketone group: 2.0%, butyl sulfhydryl group: 46.0%) , hydroxyl group content: 4.8%, Tg: 136TC, MW20_30wt% DPM solution performance evaluation: <optimal exposure amount> honing a circuit pattern substrate with a copper thickness of 35 μm by a buff roll,

After it was washed with water and dried, the thermosetting/photocurable resin composition of the above Examples 2 to 9 and Comparative Examples 1 to 4 was applied by a screen printing method at 80 ° C at 80 ° C. The hot air circulating drying oven was allowed to dry for 30 minutes. After drying, an exposure apparatus equipped with a metal halide lamp (HM W-680-G W2 0 manufactured by ORC Co., Ltd.) was used, and it was carried out by a step plate (step t ab 1 et) (Kodak No. 2). The exposure was performed so that the pattern of the ladder plate remaining in the case of 90-second development (90° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) was 6 segments, and the optimum exposure amount was obtained. Characteristic test: <solder heat resistance> The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with a modified alcohol. The swelling and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows. 〇: 1 immersion once a second, no peeling. △ : 1 time immersion in 5 seconds, no peeling. X: The film was immersed once in 5 seconds, and the photoresist layer was swollen and peeled off. <Flameability> The composition of each of the examples and the comparative examples was completely coated by screen printing on a 12:5 μm or 25 μm thick polyimine film (Kapton 100H, 50H manufactured by DuPont-Toray Co., Ltd.). , dry at 80 ° C for 20 minutes, and then left to cool to room temperature. Further, the inside was uniformly coated by screen printing, dried at 80 ° C for 20 minutes, and then left to cool to room temperature to obtain a substrate coated on both sides. The substrate of Example 1 was heat-cured at 150 ° C for 60 minutes as an evaluation sample. Further, the bases of Examples 2 to 9 and Comparative Examples 1 to 4 were used in an exposure apparatus (HMW-6 80-GW2 0) equipped with a metal halide lamp, and the solder resist was exposed at an optimum exposure amount. The lwt% Na2CO3 aqueous solution at 30 ° C was developed for 90 seconds under the conditions of spray pressure of 2 MPa, and heat-hardened at 150 ° C for 60 minutes as an evaluation sample. This flame retardancy evaluation sample was subjected to a thin vertical burning test in accordance with the UL94 specification. The evaluation is based on the UL94 specification and is shown as VTM-0 or NG (VTM-0 means not reached). <Flexibility (Folding Resistance)> The compositions of the respective Examples and Comparative Examples were screen-printed on a 25 μm thick polyimine film (Kapton 100H manufactured by DuPont-Toray Co., Ltd.). After drying at 80 ° C for 30 minutes, it was left to cool to room temperature. The substrate of Example 1 was thermally cured at 150 ° C for 60 minutes as an evaluation sample. On the other hand, in the substrates of Examples 2 to 9 and Comparative Examples 1 to 4, the exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp was used to expose the solder resist at an optimum exposure amount, and 3 (TC% wt% Na2C03) The aqueous solution was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds, and thermally cured at 150 ° C for 60 minutes as an evaluation sample. The obtained evaluation sample was repeated 180 times by seam folding. The curve was observed by visual inspection and optical microscopy (magnification x200) at the time of occurrence of cracks in the cover layup, and the number of times the crack did not occur was evaluated. The results of the above evaluation tests are shown in Table 2. -53- 201105720 [Table 2] Characteristic example than dumplings 1 2 3 4 5 6 7 8 9 1 2 3 4 Solder heat resistance Δ ο ο 0 Ο ο Ο Ο Ο ο 雠 25^m VTIH) VTB-0 vm -o VTIH) νηι-ο VTB-0 VTtt-0 mo VTIH) VTIH) m VTIH) NG Although 12.5 μ m VT1H» VT1H) VTlhO VTIH) VTIH) VTIH) VTflhO VTB-0 VTIH) VTIN) NG νηι-ο Ν6 Flexibility 7 times 5 times 5 times 4 times 4 times 5 times 5 times 5 times β times « times 1 times 5 times Example 1 0~1 7 Table 1 The composition shown in Examples 2 to 9 was prepared by diluting a flame retardant photocurable resin composition prepared without using an anthrone-based antifoaming agent with methyl ethyl ketone, and coating it on a carrier film. The photosensitive resin composition layer having a thickness of 20 μm was formed by heating and drying, and the coated film was bonded thereon to obtain a dry film. Thereafter, the coated film was peeled off, and the film was bonded to the copper-plated substrate on which the pattern was formed using a laminator. On this substrate, an exposure device (HMW-680-GW2 0) equipped with a metal halide lamp was used to expose the solder resist pattern at an optimum exposure amount, and after removing the carrier film, a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C was used. The spray pressure was measured at a pressure of 2 MPa for 90 seconds to obtain a photoresist pattern. Thereafter, the mixture was heat-cured at 60 ° C in a hot air dryer for 60 minutes to prepare a test substrate. The test substrate having the cured film obtained was subjected to the same test method and evaluation method as described above, and the evaluation test of each characteristic was carried out. The results of the respective evaluation tests were shown in Table 3.

-54 - 201105720 [Table 3] Characteristic Example 1 0 11 1 2 13 14 15 1 6 17 Example 2 Matching Example 3 Matching Example 4 Matching Example 5 Matching Example 6 Matching Example 7 Matching Example 8 with the matching example 9 solder heat resistance 0 〇 0 0 〇〇〇〇 flame retardancy 15 um VTH-0 VTB-0 VTM-0 VT1I-0 VTtt-0 VTIH) VTIH) VTB-0 Flame retardant 12.5 VTB-0 VTH-0 VTIH) VTU-0 VTH-0 VTM-0 VTU-0 VTH-0 Flexibility 7 times 6 times 5 times 5 times 7 times 7 times 6 times 7 times tL S 1 - 55-

Claims (1)

201105720 VII. Patent application scope 1. A curable resin composition characterized by (A) a carboxyl group-containing resin, (B) aluminum hydroxide, and (C) true spherical cerium oxide. (2) A curable resin composition according to the first aspect of the invention, which further comprises (D) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in the molecule. 3. The curable resin composition of claim 1, which further comprises (E) a compound containing phosphorus. 4. The curable resin composition according to claim 1, which further comprises (F) a photopolymerization initiator and (G) a photopolymerizable monomer. 5. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) has a biphenol novolak structure and an ethylenically unsaturated group. 7. The curable resin composition according to claim 2, wherein the thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule has a biphenol Epoxy resin of aldehyde varnish skeleton. 8. The curable resin composition according to any one of claims 1 to 7, which is a solder resist. 9. A dry film characterized by any one of claims 1 to 7. The curable resin composition is coated and dried on a film. -56-201105720 1 0. A cured product obtained by coating and drying a curable resin composition according to any one of claims 1 to 7 on a substrate, or The curable resin composition described above is obtained by applying a dry film which is dried on a film, and a dried coating film obtained by laminating the film onto a substrate, and performing thermal curing and/or photocuring. 1 1 A printed wiring board characterized by having a cured product of the item 10 of the aforementioned patent application. 【 -57- 201105720 IV. Designated representative map: (1) The representative representative of the case is: No (2), the symbol of the representative figure is simple: No-3-70505720 V. If there is a chemical formula in this case, please reveal the most Chemical formula that can show the characteristics of the invention: none