TW201105742A - 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 coloring agent and a flame retardant, which is a curable resin composition that can form a solder resist layer of low warpage and of excellent concealment effect on appearance defects caused by decoloration due to oxidation of copper circuits; a dry film using the same, and a printed circuit board in which the flame retarding cured film such as the solder resist are formed by the curable resin composition. The curable resin composition includes (A) resin including a carboxyl group, (B) titanium oxide, (C) aluminum hydroxide. The curable resin composition further contains (D) a thermal curable component including two or more cyclic ether groups and/or cyclic thioether groups in addition to the aforementioned components to form a thermal curable resin composition. The thermal curable resin composition further contains (F) light polymerization initiator, (G) a light polymerization monomer to form a light curable thermal curable resin composition, and preferably contains (E) a phosphorus-containing compound.

Description

[Technical Field] The present invention relates to a curable resin composition which can form a curable resin composition, particularly a solder resist which can form low bending, flame retardancy, coloring property, and concealability. Things. The present invention also relates to a dry film and a flame-retardant printed circuit board using the curable resin composition. [Prior Art] In the past, printed circuit boards and flexible circuit boards (hereinafter referred to as FPCs) have to be inflammable because they are carried on electronic equipment, and some of these solder resists are also required to be flame retardant. Among them, the FPC is generally made of a polyimide substrate, which is a film different from the printed circuit board of the glass epoxy substrate. However, in the case of the solder resist which must be applied, since the printed circuit board has the same film thickness as the FPC, the burden of the flame retardant of the solder resist is relatively large in the case of the FPC of the film. Therefore, there have been various proposals for the insufficiency of solder resists in the past. For example, JP-A-2007-1〇794 (Patent Document 1) proposes (a) an adhesive polymer, (b) a dentate aromatic ring having a bromophenyl group in a molecule, and (meth) a photopolymerizable compound of a polymerizable ethylenically unsaturated bond such as an acrylonitrile group, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus-containing compound having a phosphorus atom in a molecule The FP C is a flame retardant photosensitive resin composition. However, as a compound having a halogenated aromatic ring and a polymerizable unsaturated double bond, the use of a halogen compound is not preferable from the viewpoint of environmental load.

[S -5-201105742 Further, as a printing substrate of a film represented by FPC, when the solder resist is photocured or thermally cured, there is a problem that it is bent due to hardening shrinkage. On the other hand, the solder resist is formed for use in the protection of a copper circuit, but as one of the roles, there is no heat or moisture of the copper circuit, electrical discoloration, or scratches on the copper circuit, and dirt. Wait for the other side (hidden). In this regard, the addition of a colorant to a solder resist is generally difficult to see by increasing the concentration thereof. In recent years, from the viewpoint of the reduction of the environmentally-resistant flux, the use of a solder resist which does not have a halogen atom, and the use of a solder resist which does not have a halogen atom, has become popular in place of the chlorinated cyanine green of the conventional green coloring agent (for example, refer to Patent Document 2). ), it is clearly stated that it is not halogen-containing, so that indigo blue is used, and the blue solder resist is also used. However, compared with the green of the indigo green, the blue solder resist ink, or the green solder resist ink with the blue colorant and the yellow colorant, is less concealed and has insufficient performance as a poor appearance. The case of the function of the coloring agent which is difficult to see in the case can be known from the following description. That is, the current solder resist forms an image by photohardening, and is finally subjected to a heat hardening treatment. The temperature at this time is about 30 to 60 minutes at 150 ° C, but in practice, the temperature or time is not constant depending on the substrate label, and it is somewhat different. In particular, when the temperature is high and the treatment time is long, the substrate of the blue solder resist ink having poor concealability is used, and the discoloration caused by the oxidation of the copper circuit is prevented from being concealed, which causes a problem that the appearance of the substrate is not good. This problem occurs in the same manner as in the case of using the green solder resist ink containing the halogen-free blue colorant and the yellow colorant, and the concealability is inferior to indocyanine green -6-201105742, which is confirmed by the inventors of the present invention. Further, when the seal ink is applied to the substrate, after the solder resist is cured, the stamp is further printed and hardened, and the discoloration of the copper circuit is accelerated, and the problem of appearance becomes more serious. Further, when the substrate to be repaired during thermal hardening of the solder resist is bent, pressure and heat are sometimes applied, and discoloration of the circuit is regarded as a problem. The most unfavorable phenomenon in the discoloration of these copper circuits is that even on the same copper circuit, only the edge of the circuit (where the protective layer is thinned) exhibits a discolored state. In such a state, when the substrate is inspected or mounted, it does not conform to the inspection data and causes a problem. On the other hand, although discoloration was confirmed, if this was recognized on the copper circuit and the other portions were uniform, such a problem would not occur. These defects are more pronounced in the past, especially when replacing the indigo green color with a coloring agent such as indigo blue which does not have a halogen atom (the coloring agent is not halogenated). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-10794 (Patent Application) [Patent Document 2] JP-A-2000-7974 (Patent Application) As a matter of the foregoing prior art, the main object of the present invention is to provide a curable resin composition containing a halogen-free coloring agent and a flame retardant, which is a discoloration which can form a low curvature and is oxidized by a copper circuit. A curable resin composition of a solder resist layer which is excellent in concealability due to poor appearance. Further, an object of the present invention is to provide a dry film having low bending, flame retardancy, coloring property, and concealability, and a printed circuit board having a flame retardant film having such excellent characteristics by using the curable resin composition. . In order to achieve the above object, the present invention provides a curable resin composition comprising (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) aluminum hydroxide. In addition, the other components are contained. In addition, a thermosetting resin composition containing (D) a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group in the molecule can be used. For the other preferred form, further contains (E) a phosphorus-containing compound. In another form, the photocurable thermosetting resin composition is further contained by further containing (F) a photopolymerization initiator and (G) a photopolymerizable monomer. In another preferred embodiment, the color former (H) other than the titanium oxide (B) is contained. In a more preferred form, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane skeleton or a carboxyl group-containing resin having a biphenol novolak structure and an ethylenically unsaturated group, The thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule is an epoxy resin having a biphenol novolak skeleton. Such a curable resin composition can be applied to the formation of a solder resist of a printed circuit board. Moreover, the present invention provides a dry film obtained by applying the curable resin composition to a film and drying the film, or further applying the curable resin composition or the curable resin composition to the carrier film and drying the film. The obtained dry film is subjected to heat hardening and/or hardening obtained by photohardening. Further, the present invention provides a printed circuit board having the foregoing cured product. 201105742 EFFECT OF THE INVENTION The curable resin composition of the present invention contains (B) a carboxyl group-containing resin and (B) titanium oxide and (C) aluminum hydroxide, preferably further containing (E) phosphorus. The compound can form a film having a low environmental load, a flame retardancy, and low bending, coloring property, and concealability under a halogen-free composition. Therefore, by using the curable resin composition of the present invention, it is possible to provide a dry film having low bending, flame retardancy, coloring property, and concealability, and a printed circuit board having a flame retardant solder resist film having such excellent characteristics. MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have obtained the oxidation of the component of the curable resin composition of the present invention together with the resin containing a carboxyl group (A) and aluminum hydroxide (C). Titanium (B), even when using a non-halogen-containing coloring agent, has the effect of reducing the discoloration of the cured film, and also has the effect of reducing the curvature of the cured film. This is an unexpectedly unexpected effect in the past. When aluminum hydroxide (C) was used in combination with titanium oxide (B), it was found that aluminum hydroxide not only functions as a heat-inhibiting agent, but also has affinity with a photosensitive resin when combined with a photosensitive resin composition, and the refractive index is higher. Recently, photohardening can be performed efficiently, and the sensitivity or resolution of the addition of titanium oxide can be greatly suppressed. When a carboxyl group-containing urethane resin is used as the carboxyl group-containing resin (A), it has an effect of low elasticity and low bending, and has an effect of further reducing the curvature of the cured film by further containing a phosphorus-containing compound. (E), the flame retardancy can be further improved. Hereinafter, each constituent component of the curable resin composition of the present invention will be described in detail in -9-201105742. The carboxyl group-containing resin (A) contained in the curable resin composition of the present invention can be used for a known conventional resin compound containing a carboxyl group in a molecule. Further, in the case of the alkali-developing resin composition, the carboxyl group-containing resin (A') having an ethylenically unsaturated double bond in the molecule is preferred from the viewpoint of photocurability or development resistance. The unsaturated group is preferably one derived from an acrylic acid or a methacrylic acid derivative. Further, when only a resin containing a carboxyl group which does not have an ethylenically unsaturated double bond is used, when the composition is to be photocurable, photopolymerization having two or more ethylenically unsaturated groups in the molecule to be described later must be used in combination. Monomer (G). Specific examples of the carboxyl group-containing resin (A) include the following compounds (oligomers and polymers). (1) unsaturated carboxylic acids such as (meth)acrylic acid, and styrene, α a carboxyl group-containing resin obtained by copolymerization of a compound containing an unsaturated group such as methyl styrene, a lower alkyl (meth) acrylate or isobutylene. (2) Diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate; and carboxyl group-containing diol such as dimethylolpropionic acid or dimethylolbutanoic acid a compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a phenolic property A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a hydroxyl group or an alcoholic hydroxyl group. (3) Diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate-10-201105742 compound, polycarbonate polyol, polyether polyol, poly Polyaddition reaction of diol compounds such as ester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group A urethane resin having a carboxyl group at the terminal formed by reacting an acid anhydride at the end of the urethane resin. (4) By diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol s type epoxy resin, bisxylenol type epoxy resin A photosensitive carboxyl group-containing amine obtained by a polyaddition reaction of a (meth) acrylate or a partial acid anhydride denatured product thereof, a diol compound containing a carboxyl group, and a diol compound, such as a bisphenol type epoxy resin Carbamate resin. (5) In the resin synthesis of the above (2) or (4), a compound having one hydroxyl group and one or more (meth)acrylonyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added to the terminal. A (meth)acrylated carboxyl group-containing urethane resin. (6) In the resin synthesis of the above (2) or (4), one isocyanate group and one or more (meth) groups are added to a molecule such as a molar reaction product such as isophorone diisocyanate or pentaerythritol triacrylate. A compound of an acrylonitrile group, which is a terminal (meth) acrylated carboxyl group-containing urethane resin. (7) reacting a polyfunctional (solid) epoxy resin as described later with (meth)acrylic acid to add phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrogen to the hydroxyl group present in the side chain. A photosensitive resin containing a carboxyl group such as phthalic anhydride or the like. -11 - 201105742 (8) A polyfunctional epoxy resin which epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a hydroxyl group on the resulting hydroxyl group. 2 Photosensitive resin containing a carboxyl group. (9) A bifunctional oxetane resin to be described later is reacted with a dicarboxylic acid to form a polyester resin in which a carboxyl group of 2 alkali anhydride is added to the produced first-order hydroxyl group. (10) The resin of the above (1) to (9) is further added with an epoxy group such as a glycidyl (meth) acrylate or an α-methyl propyl propyl (meth) acrylate. A photosensitive resin containing a carboxyl group formed of a compound having one or more (meth)acryl fluorenyl groups. Among these carboxyl group-containing resins, (X) a carboxyl group-containing polyurethane resin, particularly an isocyanate group in which the urethane resin has an isocyanate group (also containing a diisocyanate) is not directly bonded. The polyfunctional epoxy resin used in the synthesis of the aforementioned resin is a bisphenol fluorene structure, a bisphenol F structure, a bisphenol structure, a biphenol novolak structure, a bisxylenol structure, In particular, when it is a compound having a biphenyl novolak structure and the hydrogenated compound, it is preferably from the viewpoint of low bending and flexural resistance. Further, among them, a carboxyl group-containing urethane in which the isocyanate group of the above-mentioned copolymerized resin or the compound having the above isocyanate group (including a diisocyanate) is not directly bonded to the diisocyanate of the benzene ring is preferable. The resin is particularly excellent in low bending, and has no yellowing, and is excellent in concealability and has low ultraviolet absorption. Therefore, it is excellent in resolution when it is an alkali-developing composition. -12- 201105742 Also, in the present specification, the term "(meth)acrylate" is a generic term for acrylate, methacrylate, and these mixtures, and the same applies to other similar expressions. As described above, the carboxyl group-containing resin (A) has a large number of free carboxyl groups in the side chain of the back bone polymer, and thus becomes a crosslinking point at the time of heat curing. Further, when it is a photosensitive composition, it is possible to develop an image by an 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 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 development becomes difficult. On the other hand, when it exceeds 200 mgKOH/g, it is carried out by a developing solution. The dissolution of the exposed portion, the line (line) will be thinner than necessary, or depending on the situation, the exposed portion and the unexposed portion are separated and the imaging liquid is dissolved and stripped, and the depiction of the normal photoresist pattern becomes difficult without good. Further, the weight average molecular weight of the carboxyl group-containing resin (A) differs depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, preferably 5,000 to 10,000,000. If the weight average molecular weight is less than 2,000, the heat resistance may be insufficient. On the other hand, when the weight average molecular weight exceeds 150,000, the storage stability deteriorates. As described above, the amount of the carboxyl group-containing resin (A) is from 5 to 60% by mass, preferably from 10 to 60% by mass, more preferably from 20 to 60% by mass, particularly preferably from 3 to 5 % by weight based on the total composition. 0% by mass. When it is less than the above range, it is not preferable because the film strength is lowered. On the other hand, when the amount is more than the above range, the viscosity of the composition of -13 to 201105742 becomes high, and the coatability and the like are lowered, which is not preferable. The titanium oxide (B) used in the curable resin composition of the present invention can be produced by a sulfuric acid method or a salt method, or by rutile type titanium oxide, anatase type titanium oxide, or water. The metal oxide is subjected to a surface treatment, and the surface-treated titanium oxide is applied by an organic compound. Among these titanium oxides (B), rutile-type titanium oxide is also preferred. The anatase type titanium oxide is often used in comparison with the rutile type because of its high whiteness. However, since the anatase type titanium oxide has photocatalytic activity, it causes discoloration of the resin in the photocurable thermosetting resin composition. On the other hand, the rutile-type titanium oxide has a certain degree of deterioration in whiteness compared with the anatase type, and since it has almost no photoactivity, a stable solder resist film can be obtained. As the rutile-type titanium oxide, a known rutile type can be used. Specifically, it is possible to use R-550, R-550, R-58 0 'R-63 0 ' R-8 20 made by Fuji Titanium Industry Co., Ltd., TR-600, TR-700, TR-750, TR-840, Ishihara Satoshi Co., Ltd. , CR-50, CR-60, CR-90, CR-97, titanium industry (stock) KR-270, KR-3 10, KR-3 80 and so on. Among these rutile-type titanium oxides, when titanium oxide having a surface treated with aqueous alumina or aluminum hydroxide is used, it is particularly preferable from the viewpoints of dispersibility, storage stability, and flame retardancy in the composition. . The amount of the titanium oxide (B) is preferably from 0. 1 to 20 parts by mass, more preferably from 1 to 1 part by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). Good for 3 to 80 parts by mass. When the amount of titanium oxide (yttrium) is less than 0.1 part by mass, good concealability and low bendability cannot be obtained. On the other hand, when it is excessively added in excess of 200 parts by mass, the titanium oxide has a property of reflecting light in the ultraviolet region, and the refractive index -14 - 201105742 is also 2.7 1 which is very high in comparison with the photosensitive resin, so When the solder resist is used, a sufficient depth of hardening cannot be obtained, and the resolution is also deteriorated. Further, according to the present invention, if aluminum hydroxide (C) is not further added, it is confirmed that the resolution is remarkably lowered. Aluminum hydroxide (C) is known as a flame retardant additive, but has a refractive index close to that of a photosensitive resin, and can be efficiently cured by photohardening. Although the titanium oxide is excellent in whiteness and concealability, the refractive index (2.71) is high, and the reflection of ultraviolet rays is also strong. Therefore, when a large amount is used, a thick film (about 1 〇 to 50 μηι) such as a solder resist is used. A decrease in sensitivity and resolution of a photosensitive composition required for resolution is a problem. Therefore, aluminum hydroxide is used together with titanium oxide, and it is intended to transmit sufficient light in the depth direction of the photosensitive resin. According to this method, the resolution of the alkali-developing photosensitive composition can be improved under the concealing property. In addition, the flame retardancy required for the solder resist can be ensured. As the aluminum hydroxide (C), those widely used can be used. For example, Higilite series, HW, Η21, Η31, H3 2, H42M, H43M, etc., manufactured by Showa Denko KK can be used. Further, the finer the particle size of the aluminum hydroxide, the more the folding resistance is. Therefore, it is preferably subjected to bead honing or the like together with a solvent or a resin to be dispersed to a primary particle diameter, and it is preferably selected by filtration or the like to be 3 μηι or more. When it is 1 μm or more, it is preferable from the viewpoint of flame retardancy and flexibility of the obtained hardened film.

The amount of the aluminum hydroxide (C) to be added is preferably from 1 to 200 parts by mass, preferably from 1 to 100 parts by mass, more preferably from 10 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A). 80 parts by mass. When the amount of aluminum hydroxide (C -15-201105742) is less than 1 part by mass, the resolution cannot be effectively improved, and the flame retardancy is also insufficient. On the other hand, when it is more than 200 parts by mass, although the flame retardancy is good, the flexibility is inferior and the soldering heat resistance is also inferior. The thermosetting component (D) which is used for the purpose of combining the composition of the present invention with a thermosetting resin composition to improve properties such as heat resistance and insulation reliability can be reacted with a carboxyl group of a carboxyl group-containing resin. Any of the conventionally known compounds having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in the molecule, but also having an epoxy having two or more functionalities The resin is particularly preferably an epoxy resin having a biphenyl aldehyde varnish skeleton. Examples of the epoxy resin having a biphenyl novolak skeleton include NC-3 00 0L, NC-3000, NC-3 000H, NC-3 100, and the like manufactured by Nippon Kayaku Co., Ltd. In the thermosetting resin composition of the present invention, the thermosetting component having two or more cyclic (thio)ether groups in the molecule which can be used as the thermosetting component is two or more molecules in the molecule. a compound having one or two types of a cyclic ether group or a cyclic thioether group of 4 or 5 membered rings, for example, a compound having two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound (D- 1) a compound having two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in a molecule, that is, an episulfide compound Examples of the resin (D·3) and the like include the above-mentioned polyfunctional epoxy compound (D-1), and examples thereof include jER828, jER8 34, jER1001, and jER1004 manufactured by Epoxy Epoxy Co., Ltd., and EPICLON 840 manufactured by DIC Corporation. EPICLON85 0, EPICLON 1050 -16- 201105742, EPICLON 2055, Epotot YD-Oll, YD-013, YD-127, YD-128, DER317, DER331, DER661, DE manufactured by The Dow Chemical Company 'R.664, ciba specialty chemicals Compa Araldite607 1 by Arny, Araldite 6084, Araldite GY250, Araldite GY260, Sumi-epoxy ESA-01 1 by Sumitomo Chemical Industries, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661 manufactured by Asahi Kasei Kogyo Co., Ltd. , AER 664 (all are trade names) bisphenol A epoxy resin; Japan Epoxy resin company jER YL903, DIC company EPICLON152, EPICLON165, Dongdu Chemical Co., Ltd. Ep otot YDB - 400, YD B-500, D. E · R · 5 4 by The Dow Chemical C omp any 2. Araldite 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-epoxy ESB-400 ' ESB-700 manufactured by Sumitomo Chemical Industries, Ltd., Asahi Kasei Industrial Co., Ltd. Company's eight.£.11.711, into ^.714 (both trade names) brominated epoxy resin; Japan Epoxy resin company jER152, jER154, The Dow Chemical C o mp an y system D. E N · 4 3 1, DEN438, DIC company EPICLONN-730, EPICLONN-770, EPICLONN-865, Dongdu Chemical Co., Ltd. Epotot YDCN-701, YDCN-704, Ciba specialty chemicals C o mp an y A ra 1 dite E CN 1 2 3 5, AralditeECN 1273, AralditeECN 1 2 99, AralditeXP Y3 07, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S 'RE-306, manufactured by Sakamoto Chemical Co., Ltd., manufactured by Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, and the phenolic varnish type epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd. into the ".11" 〇]^-2 3 5, ECN-2 99 (all are trade names); 17-201105742 EPICLON 83 0 manufactured by DIC Corporation, jER807 manufactured by Sakamoto Epoxy Co., Ltd., Epotot YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldite XPY306 manufactured by Ciba Specialty Chemicals Co., Ltd. Bisphenol F-type epoxy resin of the product name: Hydrogenated bisphenol A type epoxy resin such as Epotot ST-2004, ST-2 007, ST-3 000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; Japan Epoxy Resin Co., Ltd. Eppot YH-434 manufactured by Dongdu Chemical Co., Ltd., Araldite MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxypropylamine epoxy Resin; Araldite CY by Ciba Specialty Chemicals Company -3 50 (trade name), etc. Ethylene-type epoxy resin; Celoxide 202-1 manufactured by Daicel Chemical Industry Co., Ltd., Araldite CY175, CY179, etc. (both trade names) manufactured by Ciba Specialty Chemicals Co., Ltd. YL-93 3 manufactured by Nippon Epoxy Co., Ltd., T.E.N., EPPN-501, EPPN-502, etc. (all are trade names) manufactured by The D 〇w Chemi c al C 〇mp an y Hydroxyphenylmethane type epoxy resin: bis-xylenol type or bisphenol type epoxy resin or a mixture thereof such as YL-6056, YX-4000, YL-6121 (all trade name) manufactured by Nippon Epoxy Co., Ltd. : EBPS-2 00 manufactured by Nippon Kasei Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation; jER157S manufactured by Nippon Epoxy Co., Ltd. Name) bisphenol A novolac type epoxy resin; jER YL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 (all are trade names) of tetraphenylolethane type epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd.; Ciba specialty - 18- 201105742 chemicals company Araldite PT810 Heterogeneous epoxy resin such as TEPIC (both trade name) manufactured by Nissan Chemical Industries Co., Ltd.; diglycidyl phthalate resin such as Blemmer DGT manufactured by Nippon Oil & Fats Co., Ltd.; ZX- 1 063 manufactured by Dongdu Chemical Co., Ltd., etc. Epoxypropyl xylylene ethane hydride resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700, etc. ; 〇1 (: epoxy resin with dicyclopentadiene skeleton such as 1^-7200, ^^-720011 manufactured by the company; epoxy methacrylates such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Polymeric epoxy resin; and copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB- made by Daicel Chemical Industry Co., Ltd.) 3600 or the like), CTBN modified epoxy resin (for example, YR-102, YR-45 0 manufactured by Tosho Kasei Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among them, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferably used as the above polyfunctional oxetane compound (D-2). Illustrative of bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] Ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetane) Methoxy)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 these oligomers or [ -19- 201105742 In addition to polyfunctional oxetane such as polymers, oxetane and furfural varnish resins, poly(p-hydroxystyrene), and car do bisphenols may also be mentioned. An aromatic hydrocarbon such as a calixarene resorcinol calixarene or a resin having a hydroxyl group such as sesquioxanes. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. Examples of the episulfide resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule include bisphenol A type episulfide resin YL7 000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide resin in which an oxygen atom of an epoxy group of a furfural-type epoxy resin is substituted with a sulfur atom or the like can be used by 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 cyclic (thio)ether group in terms of 1 equivalent of the carboxyl group of the carboxyl group-containing resin. It is in the range of 0.6 to 2.5 equivalents, preferably 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, a carboxyl group remains in the solder resist film to impart heat resistance, alkali resistance, electrical insulation, and the like. It is not good to lower. On the other hand, when it exceeds 2.5 equivalents, the cyclic (thio)ether group having a low molecular weight remains on the dried coating film, so that the strength of the coating film and the like are lowered, which is not preferable. The curable resin composition of the present invention is 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, a benzotrimeric-20-201105742 cyanamide resin, or a cyclic carbonate compound may be added. A known thermosetting resin such as a bismaleimide, a 1,4-oxazepine compound, an oxazoline compound, or a carbodiimide resin. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound or two or more in one molecule. A compound having a blocked isocyanate group, that is, a blocked isocyanate compound, etc. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and hydrazine. -xylene diisocyanate, m-xylene diisocyanate and 2,4-toluene 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, the adducts 'biuret and isocyanate of the above-mentioned isocyanate compound are mentioned. The blocked isocyanate group contained in the above-mentioned blocked isocyanate compound is such that the isocyanate group is protected by reaction with a block agent, which is a temporarily inerted group. Upon heating to a predetermined temperature, the block agent is cleaved to form an isocyanate group. -21 - 201105742 As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and a cyanate block agent is used. Examples of the isocyanate compound obtained by inversely reacting with the block agent include an isocyanate type, a biuret type, and addition molding. As the isocyanate compound, for example, an aromatic poly-cyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate is used. Specific examples of the scented polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate@ include the compounds exemplified above. Examples of the isocyanate block agent include phenolic blockers such as phenol, cresol, dipyridyl, chlorophenol, and ethylphenol; ε-caprolactam, δ-pentalin, and γ-butyl Intrinsic amine blockers such as indoleamine and β-propionalamine; active methyl group blockers such as ethyl acetate and acetamidine; methanol, ethanol, propanol, butanol, and amyl alcohol , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, glycolic acid methyl Alcohol blocker such as butyl glycol, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime 'diethyl fluorenyl monohydrazine, ring a thiol blocker such as hexane hydrazine; a thiol blocker such as butyl thiol, hexyl thiol, t-butyl thiol, thiophenol, methyl thiophenol or ethyl thiophenol: decyl acetate, An acid amide group block such as benzamide; an imide block agent such as succinimide or maleimide; an amine system such as xylidine, aniline, butylamine or dibutylamine Segmental agent; imidazole, 2-ethylimidazole, etc. Blocking agent; an imine blocker such as methylimine or propylimine. The blocked isocyanate compound may be sold, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1 265, Desmodur -22-201105742 TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 21 1 7 ,

Desmotherm2170, Desmotherm2265 (above is the trade name of Sumitomo Bayeramide), Coronate2512, Coronate2513, C〇r〇nate2520 (above is the trade name of Japan Polyurethane Industry Co., Ltd.), B-830 'B-815, B-846, B-870, B-874, B-882 (trade name made by Mitsui Takeda Chemical Co., Ltd.), Ding? Eight 38〇£, 178-6 0PX, E4 02-B8 0T (trade name made by Asahi Kasei Chemical Co., Ltd.), etc. Further, Sumidur BL-3175 and BL-4265 were 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 from 1 to 100 parts by mass, preferably from 2 parts by mass to 100 parts by mass of the carboxyl group-containing resin (A). A ratio of 70 parts by mass is appropriate. When the amount of the compounding amount is less than 1 part by mass, the strong toughness of the sufficient coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the preservation stability of the composition may be lowered. Further, examples of the other thermosetting component include a melamine derivative and a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, and a hydroxymethyl urea compound. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzene melamine compound, an alkoxymethylated acetylene urea compound, and an alkoxymethylated urea compound are obtained by using each methylol melamine The compound, the methylol benzene melamine compound, the methylol acetylene-23-201105742 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 examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly preferred is a melamine derivative having a formaldehyde water concentration of 0.2% or less which is preferable to the human body or the environment. Examples of such merchandises include Cymel 3 00, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. Same as 1156' with 1158' with 1123, with 1170, with 1174, with UFR65, with 300 (above, Mitsui Cyanamid (share) system), Nikalac Mx-75 0, with Mx-03 2, with Mx-270, with Mx -2 80, with Mx-290, with Mx-706, with Mx-708, with Mx-40, with Mx-31, with Ms-11, with Mw-30' with Mw-30HM, with Mw-390, with Mw-l〇〇LM, same as Mw-750LM (above, Sanhe Chemical Co., Ltd.). 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 include a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and hydrazine. Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1·(2-cyanoethyl)-2-ethyl-4-imidazole: dicyanodiamine, benzyldimethyl Amine, 4-(dimethylamino)-hydrazine, hydrazine-dimethylbenzylamine, 4-methoxy-hydrazine, hydrazine-dimethylbenzylamine, 4-methyl hydrazine, hydrazine An amine compound such as dimethylbenzylamine, an anthracene compound such as hexanoic acid diterpene or azelaic acid diphosphate; a phosphating-24-201105742 compound such as triphenylphosphine, etc., and being sold as a seller, for example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemicals Co., Ltd., U-CAT (registered trademark) 35 03N, manufactured by San-Apro Co., Ltd. U-CAT3502T (all trade name of block isocyanate compound of dimethylamine), 〇811, 〇3]^, 1;-€八丁3八102,1;-CAT 5 002 (all are two-ring type 脒Compounds and their salts) and the like. Although it is not particularly limited, if it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction which promotes an epoxy group and/or an oxetanyl group and a carboxyl group, it can be used individually or It can be used in combination of 2 or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-ethylidene-2,4 are also used. -diamino-S-trisyl, 2-vinyl-4,6-diamino-S-triazine·trimeric isocyanate adduct, 2,4-diamino-6-methylpropene An S-triazine derivative such as a methoxyethyl-S-triazine-triisocyanate adduct, preferably a compound which functions as an adhesion imparting agent and the above-mentioned thermosetting catalyst And use it. The amount of the thermosetting catalyst is sufficient in a usual amount ratio, for example, 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the above-mentioned mercapto group-containing resin (A). . The curable resin composition of the present invention preferably contains a phosphorus-containing compound (E). As a phosphorus-containing compound, it is preferred to use it as an organic phosphorus-based flame retardant. It is preferably a phosphoric acid vinegar and a condensed phosphate ester, a cyclic phosphorus-nitrogen compound, a phosphorus-nitrogen oligomer, a phosphonate or the following - Compound of formula (I) 0 -25- 201105742 [Chemical 1]

In the formula R3, R1, R2 and R3 are each independently and represent a substituent other than a halogen atom. As a commercial product of the compound of the above formula (I), there are A 'SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanguang). The particularly preferred phosphorus-containing compound (E) used in the present invention may, for example, be one having (1) an acrylate group, or (2) having a phenolic hydroxyl group, or (3) an oligomer or a reactive group. A polymer, (4) a phosphorus-nitrogen oligomer, and (5) a phosphonate. (1) Phosphorus-containing compound having an acrylate group The acrylate having a phosphorus element is preferably a compound having a phosphorus element and having two or more (meth) acrylates in the molecule. Specifically, the above general formula (1) In the case where ^ and 8.2 are hydrogen atoms, and r3 is a compound of an acrylate derivative, generally 9,10-hydrogen-9-che-10-tenfi-10-oxide is conventionally used. It is synthesized by a Michael addition reaction of a functional acrylic acid ester monomer. Examples of the above-mentioned known acrylic acid acetal monomer are exemplified by ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and the like, and propylene glycol -26-201105742; Polyols such as diol, trimethylolpropane, pentaerythritol, dipentaerythritol, and para-hydroxyethyl isocyanate or polyvalent acrylics such as these ethylene oxide adducts, propylene oxide adducts or caprolactone adducts Esters; phenoxy acrylates, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; and amine groups of the above polyalcohols Polyvalent acrylates of glycopropyl ethers such as formate acrylates, glycerol diglycidyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triepoxypropyl isocyanate And melamine acrylate, and/or methacrylates corresponding to the above acrylates, etc. (2) phosphorus-containing compounds having a phenolic hydroxyl group, phosphorus-containing compounds having the phenolic hydroxyl group, and hydrophobicity and heat resistance thereof Higher' and no electrical characteristic drop by hydrolysis , Solder heat resistance is high. Further, as a preferred combination, (D) reacts with an epoxy resin by using an epoxy resin or other epoxy resin having a biphenyl skeleton as a component, and is incorporated into the network, so that it can be hardened without being externally The advantage of leakage. As a merchandise, there are HCA-HQ, etc., which is manufactured by Sanguang Co., Ltd. (3) Phosphorus-containing compounds of oligomers or polymer oligomers or polymers, the flexurality is less reduced by the influence of the alkyl chain, and the molecular weight is large, and no hardening occurs after hardening. Advantages of the goods, as a merchandise, there are three light (shares) system M_Ester_Hp, Toyobo (stock) system, including the Byron337. (4) Phosphorus-nitrogen-based oligomers are effective as phenoxy-based compounds as ortho-nitrogen oligomers, having -27-201105742 substituted or unsubstituted phenoxyphosphazene oligomers or triads, 4 ring body of 5 body, 5 body, although liquid or solid powder can be applied. As a vending product, there are FP-100, FP-300, FP-390, etc. manufactured by Fushimi Pharmaceutical Co., Ltd., and phenoxyphosphorus nitrogen oligomers which are also substituted with a polar group such as an alkyl group or a hydroxyl group or a cyano group. Since the solubility of the resin containing a carboxyl group is high, even if a large amount is added, it is not preferable because it causes an improper situation such as recrystallization. (5) Phosphonate By using a phosphonate, the flame retardancy can be further improved without impairing the softness of the cured coating film. Further, by using a phosphonate having excellent heat resistance, the hot pressure at the time of mounting can suppress leakage outside the flame retardant. As the merchandise, EXOLIT OP 93 0 and EXOLIT OP 93 5 manufactured by Clariant Co., Ltd. may be mentioned. The amount of the phosphorus-containing compound (E) to be used as the flame retardant is preferably from 0 to 200 parts by mass, more preferably from 0 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). . When such a large amount is added, the flexural properties and the like of the obtained hardened film are deteriorated, which is preferable. As the photopolymerization initiator (F) constituting the photocurable resin composition of the present invention, an oxime ester photopolymerization initiator selected from the group consisting of an oxime ester group, and α-aminoethyl phthalene photopolymerization can be used. One or more kinds of photopolymerization initiators in which a starting agent and a mercaptophosphine oxide photopolymerization initiator are grouped. Examples of the oxime ester-based photopolymerization initiator include CG I-3 2 5 manufactured by Ciba Specialty chemicals C omp, Irgacure OXEO1, Irgacure OXE02, N-1919 manufactured by ADEKA, and ADEKA ARKLSNCI- 83 1 and so on. Further, a photopolymerization initiator -28-201105742 having two oxime ester groups in the molecule may be used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (Π) may be mentioned. [Chemical 2]

(wherein, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 to 8) Alkoxy group, amine group, alkylamino group having a carbon number of 1 to 8 or substituted with a dialkylamino group), naphthyl group (having an alkyl group having 1 to 17 carbon atoms, carbon number 1 to Alkoxy group of 8 or an amine group, substituted with an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group), each of which represents a hydrogen atom and an alkyl group having 1 to 17 carbon atoms; Alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, and an alkyl group having 1 to 8 carbon atoms) a substituted alkylamino or dialkylamino group, a naphthyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) Substituted by an alkylamino or dialkylamino group, a mercapto group, a pyridyl group, a benzofuranyl group, a benzothiophene group, and Ar represents a carbon number of 1 to 10, a vinyl group, a vinyl group, and a benzene group. Base, phenyl, pyridyl, stilbene, thienyl, thiol, thienyl, furanyl, 2, 5-pyrrole-diyl, 4,4'-fluorene-diyl, 4,2'-styrene-diyl' η is an integer of hydrazine or hydrazine. Particularly in the above formula, X and hydrazine are each methyl or Ethyl, hydrazine is methyl or phenyl, η is 0, Ar is phenyl, stannaphthyl, thiophene or thienyl group is better than 201105742. As α-aminoethyl phthalene photopolymerization initiator, Specific examples thereof include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1-( 4 -morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholine) Phenyl]-1-butanone, hydrazine, hydrazine-dimethylaminoethyl benzene benzene, etc. As a commercial product, Irgacure 907, Irgacure 369, Irgacure 3 manufactured by Ciba Specialty Chemicals Co., Ltd. may be mentioned. 7 9 et al. As a mercaptophosphine oxide photopolymerization initiator, specifically, 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis(2,4,6-trimethyl) Benzophenyl)-phenylphosphine oxide, bis(2,6-dimethoxyphenylhydrazine)-2,4,4-trimethyl-pentylphosphine oxide, etc. As a commodity, L from BASF Ucilin ΤΡ Ο 'Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd., etc. Among the above photopolymerization initiators, the sulfhydryl squamous oxide initiator is excellent, and it is excellent in light fading property or light permeability, and is flame retardant. In addition, the oxime ester initiator is a good initiator, and a small amount has an effect on the sensitivity improvement. Therefore, the outer gas during the heat treatment after the formation of the anti-corrosion film is less, and the film has a reduced effect on the bending of the film. Therefore, it is better. It is especially good for both. The amount of the photopolymerization initiator (F) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). appropriate. When the amount of the photopolymerization initiator (F) is less than 0.01 parts by mass, the photocurability on copper -30-201105742 may be insufficient, the coating film may be peeled off, or the coating properties such as chemical resistance may be lowered. Not good. On the other hand, when it exceeds 30 parts by mass, the light absorption of the photopolymerization initiator (F) on the surface of the solder resist coating film becomes intense, and the deep hardenability tends to be lowered. In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (II), the amount thereof is preferably 〇·〇1 to 2 for 100 parts by mass of the carboxyl group-containing resin (A). 0 parts by mass, preferably in the range of 〜.〇1 to 5 parts by mass. Other examples of the photopolymerization initiator, the photo-starting agent, and the sensitizer which are applicable to the photocurable resin composition of the present invention include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthone. A compound, a ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetophenone compound are given. For example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetamidine. Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thiophenone. Specific examples of the ketal compound include, for example, acetophenone-31 - 201105742 ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound include benzophenone, 4-phenylphenyldiphenyl sulfide, 4-benzoinyl-4'-methyldiphenyl sulfide, and 4-benzene. Mercapto-4'-ethyl-phenyl sulfide, 4-phenylindoleyl-4,-propyldiphenyl sulfide. Specific examples of the tertiary amine compound are, for example, an ethanolamine compound, a compound having a quaternary amino benzene structure, for example, 4,4,-dimethylaminobenzophenone (Nisso Cure MABP, manufactured by Nippon Soda Co., Ltd.) , 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminobenzophenone, 7-(diethylamino)-4-methyl- A dialkylamino group such as 2H-1-benzopyran-2-one (7-(diethylamino)_4-methylcoumarin) contains a coumarin compound, 4-dimethylamino benzoin Acid ethyl (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (

Quantacure DMB manufactured by International Biosynthetic Co., Ltd., 4-dimethylamino benzoic acid (η-butoxy)ethyl (Quantacure BEA, manufactured by International Biosynthetic Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (KAYACUREDMBI, manufactured by Nippon Kayaku Co., Ltd.) '4-Dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (Zhongtu Valley Chemistry) Company-made EAB). Among the above compounds, a thioxanthone compound and a tertiary amine compound are also preferred. In the composition of the present invention, when the thioxanthone compound is contained, it is preferable from the viewpoint of deep hardenability, wherein 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone are also used. A ketone compound such as 2-chlorothioxanone or 2,4-diisopropylthioxanthone-32-201105742 is preferred. The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, which is not preferable in terms of the cost of the product. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound is also used, and a dialkylamine group having a maximum absorption wavelength of 35 〇 to 4 lOnm is contained. The coumarin compound is particularly preferred. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. The dialkylamine group having a maximum absorption wavelength of 350 to 410 nm contains a coumarin compound because the maximum absorption wavelength is in the ultraviolet region, so the coloration is less, and the colorless transparent photosensitive composition is compared with the original coloring pigment to provide reflection coloration. A colored solder mask film of the color of the pigment itself. Particularly, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm, which is preferable. The amount of the above-mentioned tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the tertiary amine compound is less than 1 part by mass, the effect of sufficiently sensitizing is not obtained. On the other hand, when it exceeds 20 parts by mass, the light absorption on the surface of the coating film of the dry solder resist by the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered. In the photocurable resin composition of the present invention, in order to improve the sensitivity, -33-201105742 can be used as a well-known conventional N-phenylglycine, phenoxyacetic acid, or thiophenoxyacetic acid. , hydrothiazolidine and the like. Specific examples of the chain shifting agent include, for example, mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof. a linkage activator of a carboxyl group; a thiol group, a thiol propanol, a thiobutanol, a thiopropyl propane diol, a thiothiobutane diol, a hydroxy benzene thiol, and a derivative thereof, and the like Chain-shifting agent; 1-butane thiol, butyl-3-hydrothiopropionate, methyl-3-hydrothiopropionate, 2,2-(extended ethyldioxy)diethane Mercaptan, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, a heterocyclic compound having a thiol group which acts as a chain shifting agent such as cyclohexanethiol, thioglycerol or 4,4-thiobisbenzenethiol, and examples thereof include thiothio-4-butene. Ester (alias: 2-hydrothio-4-butyrolactone) 2-aminothio-4-methyl-4-butyrolactone, 2-sulfuryl-4-ethyl-4-butyrolactone, 2-Homothio-4-butyrolactone, 2-hydrothio-4-butylidene, N-methoxy-2-thiol- 4-butylideneamine, N-ethoxy-2-hydrothio-4-butylidene, N-methyl-2-hydrothio-4-butylidene, N-ethyl-2 -Hexylthio-4-butylidene, N-(2-methoxy)ethyl-2-hydrosulfanyl-4, butaneamine, N-(2-ethoxy)ethyl-2 -Hexylthio-4-butylidene, 2-hydrothio-5-valerolactone, 2-hydrothio-5-pentalinamide, N-methyl-2-hydrosulfanyl-5- Valentamamine, N-ethyl-2-hydrothio-5-pentalinamide, N-(2-methoxy)ethyl-2-aminosulfanyl-5-pentane, N- (2-Ethoxy)ethyl-2-nitrothio- 5-pentalinamide and 2-hydrothio-6-caprolactam. -34- 201105742 A heterocyclic compound having a thiol group as a developing mobile agent which does not impair the photocurable resin composition, and is a thiophenylbenzene 3-hydrothio-4-methyl-4H-1,2 Preferably, 4-triazole, 5-methyl-l,3,4-l mercaptan, 1-phenyl-5-hydrothio-1H-tetrazole. These chains are used alone or in combination of two or more. These photopolymerization initiators, photoinitiating aids, and sensitizers can be used in a mixture of two or more types. The photopolymerization initiator, the photo-starting agent, and the sensitizer are preferably in an amount of not more than 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the tendency to lower the deep curability is lowered by the collection. The photopolymerizable monomer (G) to be used in the photocurable resin group of the composition of the present invention is cured by an active energy ray, so that the photocurable resin composition of the present invention is insoluble in alkali or helps to dissolve it. By. Examples of such a compound include dipropylene of glycerol such as ethoxytetraethylene glycol, polyethylene glycol, and propylene glycol: hexanediol 'trimethylolpropane, pentaerythritol, diquaternary-hydroxyethyl isocyanate, and the like. Polyvalent acrylates such as alcohols or these ethylene oxide propylene oxide adducts; phenoxy propylene phenol A diacrylate; and phenolic ethylene oxide adduct alkyl adducts Esters; polyvalent acrylates of glycidyl ethers such as glycerol diglycidyl ether epoxypropyl ether, trimethylolpropane triepoxypropyl ether, tricyclocyanate, etc.; and trimerate And/or corresponding to the methacrylate ester-containing thiazole and thiadiazole-2-moving agent of the above acrylate, which can be used alone or in a total amount to form a light aqueous solution of 35 kinds of light-absorbing products. And diol, methacrylate pentaerythritol, adduct or acid ester, bis or propylene oxide, glycerol triethoxypropyl isocyanide propylene, and the like. -35-201105742 Further, a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin which reacts acrylic acid, or a hydroxyl group further than the epoxy acrylate resin, makes pentaerythritol triacrylate An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate may, for example, be mentioned. In the case of the above-mentioned epoxy acrylate-based resin, the amount of the photopolymerizable monomer (G) having two or more ethylenically unsaturated groups in the molecule can be improved without reducing the dryness of the touch. The resin (A) containing a carboxyl group has a ratio of 1 part by mass or less, preferably 5 to 70 parts by mass, per 100 parts by mass. When the amount is less than 5 parts by mass, the photocurability is lowered, and the alkali development after the irradiation of the active amount line makes it difficult to form a pattern, which is not preferable. On the other hand, when it exceeds 1 part by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable. A coloring agent (Η) can be added to the curable resin composition of the present invention. As the coloring agent (Η), a conventionally known coloring agent such as red 'blue, green, yellow, or the like may be used, and any of a pigment, a dye, and a coloring matter may be used. Specifically, the color index (C.I.: The Society of Dyers and Colourists) number is given as follows. However, it is preferable that halogen is not contained from the viewpoint of environmental load reduction and influence on the human body. Red coloring agent: As a red coloring agent, there are monoazo type, bisazo type, AZO LAKE type, benzimidazolone type, anthraquinone type, pyrrolopyrroledione type 'condensed azo-36-201105742 series, 蒽醌The system, the quinacridone system, etc., specifically, the following O monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22,23, 31, 32, 112, 1 14, 146, 147, 15 1, 170, 184, 187, 188, 192 i, 2 1 10, 245, 253, 25 8, 266, 267, 268, 269 » Bisazo: Pigment Red 37, 3 8, 4 1 ο Single AZO LAKE: Pi gment 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 〇benzimidazolone: Pigment Red 171 , Pigment Red 175, P igment Red 17 6 , P i gm e nt R ed 185 , Pi gment Red 208 o Philippine: Solveni t Red 13 5 , Solvent Red 179 , Pigment Red 123 , Pigment Red 149 , Pigment Red 166 , Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 19 4' Pigm Ent Red 224. Pyrrolopyrrolodione: Pig ment Red 254, Pigment Red 255 ' Pigment Red 264, Pig ment Red 270, Pigment Red 272 _ 0 condensed gas system · Pigment R .e d 220, P i gm ent Red 144,

Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 22 1, Pigment Red 242 Brewing: Pigment Red 168 ' Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, S ol vent Red 52, S ο 1 vent Red 2 07 o -37- 201105742 Quinoxazone: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207 ' Pigment Red 209. Blue coloring agent: As a blue coloring agent, there are anthracycline-based and anthraquinone-based, and the pigment is a compound classified as a dye (Pigment), 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, Pigment Blue 60 o As a dye system, use 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. In addition to the above, a metal substituted or unsubstituted anthraquinone compound can also be used. Green colorant: As a green colorant, there are similarly anthracycline, anthraquinone, and anthraquinone. Specific use of Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 Wait. In addition to the above, a metal substituted or unsubstituted anthraquinone compound can also be used. Yellow coloring agent: -38- 201105742 As a yellow coloring agent, there are monoazo type, bisazo type, condensed azo type, benzimidazolone type, isoindolinone type, anthraquinone type, etc. The following are available. Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202. Iso-U porphyrin lanthanide: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Y e 11 o w 1 8 5. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 12 8, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180 e Benzymidazole: Pigment Yellow 120, Pigment Yellow 15 1 , Pigment Yellow 1 54 , P i gm ent Yello w 15 6 , Pigment Yell ow 17 5, P i gm ent Yell ow 18 1 O Monoazo system: Pigment Y e 11 ow 1,2, 3, 4, 5, 6 , 9, l〇, 12, 61, 62, 62 : 1, 65, 73, 74, 7 5, 97 , 100, 104 ,l〇5, 111, 116, 167, 1 68, 1 69, 182, 183 ° Bisazo: P i gm ( 3nt Yellow 12, 13, 14, 1 t ;, 17, 55, 63, 8 1 , 83, 87, 126, 127, 152, 170, 172, 174, 176, 188 198° Others, coloring agents such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone. For specific examples, Pigment Violet 19, 23, -39-201105742 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI dye orange 1, CI dye orange 5, CI dye orange 13, cI dye orange 14, C_I' dye orange 16, C_I. dye orange 17, c.〗. Orange 24, CI dye orange 34, CI dye orange 36, CI dye orange 38, CI dye orange 40, CI dye orange 43, CI dye orange 46, CI dye orange 49, CI dye orange Color 51, CI dye orange 61, CI dye orange 63, CI · dye orange 64, CI dye orange 71, CI dye orange 73, CI dye brown 23, CI dye brown 25, CI dye black 1, CI The blending ratio of the above-mentioned coloring agent (Η) is not particularly limited, but it is preferably 〇1 to 1 part by mass for 100 parts by mass of the carboxyl group-containing resin (Α). The ratio of 0.1 to 5 parts by mass is sufficient. The curable resin composition of the present invention is intended to increase the physical strength of the coating film, etc., and may be added as necessary. As such a chelating agent, a conventionally used inorganic or organic chelating agent can be used, and in particular, barium sulfate, spheroidal cerium oxide and talc are preferably used. Further, magnesium hydroxide, boehmite, etc. may be used for the purpose of imparting flame retardancy. Further, a compound having one or more ethylenically unsaturated groups or a NANOCRYL (trade name) XP 0396 and XP 0596 manufactured by Hanse-Chemie Co., Ltd. in which the above-mentioned polyfunctional epoxy resin is dispersed may be used. XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all products Glade name), or NAN OPOX (trade name) XP 0516, XP 0525, XP 03 14 manufactured by Hanse-Chemie (all are the name of the product Glade). These may be added alone or in combination of two or more. -40-201105742 The amount of the compound to be added is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A). Share. When the amount of the chelating agent is more than 5 parts by mass, the viscosity of the curable resin composition becomes high, so that the printability is lowered, and the cured product becomes brittle and thus is not preferable. In the curable resin composition of the present invention, for the purpose of improving flexibility and dryness of the touch, a conventionally known adhesive-polymer can be used. As the binder-polymer, a cellulose-based, polyester-based or phenoxy resin-based polymer is preferred. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., and the polyester polymer is a Byron series manufactured by Toyobo Co., Ltd. Further, the phenoxy resin is preferably a phenoxy resin of bisphenol A, bisphenol F or a hydrogenated compound thereof. The amount of the adhesive-polymer 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 alkali developability of the curable resin composition is deteriorated, and the time for development is short, which is not preferable. In the curable resin composition of the present invention, in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate, an adhesion promoter can be used. Specific examples include benzazole, benzoxazole, benzothiazole, 2-hydrothiobenzimidazole '2-hydrothiobenzoxazole, 2-hydrothiobenzothiazole, 3-morpholinomethyl-i-phenyl-triazolethione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-hydrothio-5-methylsulfide- Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine group containing benzotriazole, -41 - 201105742 machine decane coupling agent, etc. Generally speaking, most of the polymer materials are first In the case of primary oxidation, the oxidative degradation of the chain is continued, and the function of the polymer material is lowered. In the curable resin composition of the present invention, it is possible to prevent oxidation, and it is possible to add (1) to cause the generated radical to be ineffective. The radical scavenger or/(2) an antioxidant such as a peroxide decomposer which decomposes the generated peroxide into a harmless substance and does not generate a new radical. Examples of the specific antioxidant include a hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, and 2,6 as an antioxidant which acts as a radical scavenger. - bis-butyl ketone-cresol, 2,2-methyl-bis(4-methyl-6-t-butylphenol), 1,1,3-parade (2_methyl_4_ Hydroxy_5_t_butylphenyl)butane, 1,3,5-trimethyl-2,4,6-gin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1 , 3,5-gin (3',5,di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1&311,511)trione An anthraquinone compound such as hemiquinone or benzoquinone; an amine compound such as bis(2,2,6,6-tetramethyl-4)piperidinyl)-sebacate or phenothiazine.

The radical scavenger may be a commercially available product, and examples thereof include ADEKA STAB AO-30 'ADEKA STAB AO-330, ADEKA STAB AO-20, ADEKA STAB LA-77, ADEKA STAB LA-57, ADEKA STAB LA-67, ADEKA STAB LA-68, ADEKA STAB LA-87 (above is the trade name of Asahi Kasei Corporation), IRGANOX1010, IRGANOX 1 03 5, IRGANOX1 076, IRGANOX1135, TINUVIN 1 1 1 FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5 100 (above, Ciba specialty -42-201105742 chemical company product name), etc. As an antioxidant which acts as a peroxide decomposer, a specific compound is a phosphorus system, such as a triphenyl phosphite. A sulfur compound such as a compound, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate or distearyl 3,3'-thiodipropionate. The peroxide decomposing agent may be a vending product, and examples thereof include ADEKA STAB TPP (trade name manufactured by Asahi Kasei Co., Ltd.), Mark AO-412S (trade name manufactured by ADEKA ARGUS Chemical Co., Ltd.), and Sumilizer TP S (manufactured by Sumitomo Chemical Co., Ltd.). Product name) and so on. These antioxidants may be used alone or in combination of two or more. In addition, in general, the polymer material absorbs light and causes decomposition and deterioration. Therefore, in the curable resin composition of the present invention, in order to stabilize the ultraviolet rays, ultraviolet rays may be used in addition to the above-mentioned antioxidants. Absorbent. Examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamic acid ester derivative, and an aminobenzoic acid. An ester derivative, a diphenylmethylmethane derivative, or the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-di. Hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. 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. Examples of the benzotriazole derivative are -43-201105742, and 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2,-hydroxy-5 are exemplified. '-Methylphenyl)benzotriazole, 2-(2,-hydroxy-3,-1-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 a commercially available product, and examples thereof include TINUVIN PS ' TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479. (The above is a trade name of Ciba specialty chemicals Company) and the like. The above-mentioned ultraviolet absorbing agent may be used alone or in combination of two or more kinds, and the molded article obtained from the curable resin composition of the present invention can be stabilized by the use of the above-mentioned antioxidant. Further, in the curable resin composition of the present invention, an organic solvent can be used in order to adjust the composition or composition of the carboxyl group-containing resin (A) or the viscosity to be applied to the substrate or the carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone: aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 赛路苏, methyl 赛苏苏, butyl 赛路苏, 卡必Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether 'dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene-44 - 201105742 diol monoethyl ether and other glycol ethers Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The organic solvent may be used singly or as a mixture of two or more. The curable resin composition of the present invention may further contain a conventionally known tackifier, fine powder of cerium oxide, organic bentonite, montmorillonite, or the like, and a conventionally used tackifier, polyfluorene, fluorine, or high. A well-known conventional additive such as an antifoaming agent such as a molecular system and/or a coating agent, an organic decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based antioxidant, or a rust preventive agent. The aforementioned thermal polymerization inhibiting agent can be used for preventing thermal polymerization or time-lapse polymerization of the above polymerizable compound. Examples of the thermal polymerization inhibiting agent include 4-methoxyanthracene, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4- Methoxy-2-hydroxybenzophenone, salinized first copper, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-Extended methyl bis(4-methyl-6-t-butylphenol:)' pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyl blue, copper Chelation with organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compounds, nitroso compounds and A1. 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 of the curable resin formed on the carrier film. In the case of dry film formation, the curable resin composition of the present invention is diluted with an organic solvent as described above, and then adjusted to an appropriate viscosity, and then a corner coater and a blade coater are used. 'Nozzle coater, bar coater, extrusion coater, reverse coater, roll coater, gravure coater, spray coater are equivalent to coating a uniform thickness on the carrier film, generally The film was obtained by drying at 50 to 13 ° C for 1 to 30 minutes. The coating film thickness is not particularly limited, and is generally selected from the range of 10 to 150 μm, preferably 20 to 60 μm, after drying, as a supporting film, using a plastic film, and using polyterephthalic acid. A plastic film such as a polyester film such as ethylene glycol ester, a polyimide film, a polyimide film, a polypropylene film or a polystyrene film is preferred. The thickness of the supporting film is not particularly limited, and is generally suitably selected in the range of 10 to 150 μm. After forming a film on the carrier film, it is preferable to prevent the film from adhering to the surface of the film, and it is preferable to laminate the peelable cover film on the surface of the film. As a peelable cover film, for example, a polyethylene film or a polytetrathene can be used. A vinyl fluoride film, a polypropylene film, a surface-treated paper, etc., when the cover film is peeled off, the adhesive force of the film and the carrier film may be smaller than the adhesion force of the film and the cover film. The curable resin composition of the present invention is adjusted, for example, to a viscosity suitable for the coating method of the organic solvent, and is applied by a dip coating method, a flow coating method, a roll coating method, or a bar coating method on a substrate. Coating by a screen printing method, a curtain coating method, etc., and then drying the organic solvent contained in the composition at a temperature of about 60 to 1 ° C (dry drying) to form a non-sticky form. Sex film. Further, when the composition is applied to a carrier film and dried to form a film after drying-46-201105742, and the film is wound into a dry film, the laminate is bonded to the machine material to form a layer of the curable resin composition and the substrate. After the material is in contact, the resin insulating layer is formed after peeling off the supporting film. In the case of a photocurable resin composition, a direct pattern is formed by a contact or a direct exposure machine with a selective active energy ray by a contact type (or a non-contact method) by forming a pattern mask. After exposure, the unexposed portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a photoresist pattern. Further, in the case where the composition containing the thermosetting component (D) is heated, for example, at a temperature of about 140 to 180 ° C, the carboxyl group and the molecule of the carboxyl group-containing resin (A) are obtained. The thermosetting component (D) having two or more cyclic ether groups and/or a cyclic thioether group reacts to form heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Excellent hardened coating film. Further, even in the case where the thermosetting component (D) is not contained, the ethylene unsaturated bond remaining in the unreacted state at the time of exposure is subjected to thermal radical polymerization by heat treatment. Purpose. For the purpose of use, heat treatment (thermosetting) can also be carried out. Examples of the substrate include a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance, and paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass, and the like are also used. Cloth/non-fiber cloth epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluorine, polystyrene, PPO, cyanate ester, and other high-frequency circuit copper-clad laminates, etc. Glade (FR-4, etc.) copper-clad laminate 'other polyimide film, PET film, glass substrate' ceramic substrate, wafer board-47-201105742, etc. The volatilization drying after the application of the curable resin composition of the present invention can be carried out using a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, or the like (using a heat source having a heating method by means of steam) The hot air in the machine is used for the flow contact method and the manner in which the nozzle is blown into the support. In the case of the photocurable resin composition, the exposed portion (the irradiation portion of the active energy ray) is subjected to exposure (irradiation of the active energy ray), and the exposed portion (the portion irradiated with the active energy ray) is hardened. . The exposure machine used for the active energy ray irradiation may be a device that irradiates ultraviolet rays in a range of 350 to 450 μm if it is a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a methyl halide lamp, a mercury short-arc lamp, or the like. Further, a direct drawing device (for example, a laser direct imaging device that directly depicts a portrait by means of computer CAD data) can be used. As the laser light 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 exposure amount used for the image formation differs depending on the film thickness and the like, but is generally in the range of 20 to 800 m J/cm 2 , preferably 20 to 600 m J/cm 2 . As the development method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, or the like can be used. An aqueous solution such as an amine. [Embodiment] [Embodiment] -48-201105742 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are based on quality unless otherwise specified. Synthesis Example 1 (A-1) Synthesis of a resin corresponding to the carboxyl group-containing resin (2): In a reaction vessel equipped with a stirring device, a thermometer, and an electric storage device, a compound having two or more alcoholic hydroxyl groups is introduced. Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (TJ5650J, manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight 800) 3600 g (4.5 m), dimethylol 814 g (5.5 mol) of butyric acid and 1 18 g (1.6 mol) of η-butanol as a molecular weight regulator (reaction stop agent). Next, the time period in which the temperature in the reaction vessel starts to decrease is stopped by heating to 60 ° C while stirring, as a trimethylhexamethylene diisocyanate 2009g (10. 8 mole) which is an isocyanate compound having no aromatic ring. The mixture was heated again, and stirring was continued at 80 ° C, and the reaction was terminated by the infrared absorption spectrum confirming that the absorption spectrum (228GCHT1 ) of the isocyanate group had disappeared. Next, carbitol acetate was added until the solid content became 60% by weight to obtain a carboxyl group-containing resin containing a viscous liquid of a diluent. The obtained carboxyl group contained a solid content of a polyurethane having an acid value of 49.8 mgKOH/g. Synthesis Example 2 (A-2) corresponds to the resin of the carboxyl group-containing resin (5) -49-201105742: In a reaction vessel equipped with a stirring device, a thermometer, and an electric storage device, the input is made of 1,5-pentane A polycarbonate diol derived from an alcohol and iota, 6-hexane diol (TJ565 (H, number average molecular weight 800) 2400 g (3 mol), dimethylolpropionic acid 6 〇 3 g, manufactured by Asahi Kasei Chemicals Co., Ltd. (45 mol) and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxy compound. 1887 g (8.5 mol) of isophorone diisocyanate as a polyisocyanate was continuously added while heating while stirring When the temperature in the reaction vessel begins to decrease, the heating is continued at 8 Torr. The absorption spectrum of the isocyanate group is confirmed by infrared absorption spectrum (22 80 (:1^1) has disappeared). The carbitol acetate was added to a solid content of 50% by mass. The acid value of the solid component of the obtained carboxyl group-containing resin was 50 mgKOH/g. Synthesis Example 3 (A-3) corresponds to the above carboxyl group-containing resin (4) Synthesis of resin: fractional burning RE310S (bifunctional bisphenol a-type epoxy resin, epoxy equivalent: 184 g/eq) manufactured by a bisphenol A-type epoxy compound (368.0 g), acrylic acid (molecular weight: 72.06) 142.7 g, 2.94 g of 2,6•di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 153 g of triphenylphosphine as a reaction catalyst, reacted at a temperature of 98. The acid value of the liquid is 0 to 5 mgKOH/g or less to obtain an epoxy carboxylic acid ester compound (a) (theoretical molecular weight: 510.7). Next, at -50 to 201105742, the reaction liquid is added with carbitol acetate as a reaction solvent. 588.2 g, dimethylolpropionic acid (b) (molecular weight: 134.16) 105.5 g, and the temperature is raised to 451. Do not slowly drop the isophorone diisocyanate (c) into the solution at a reaction temperature exceeding 65 ° C (molecular weight : 222.28) 264.7g. After the end of the dropping, the temperature is raised to 8 (TC, according to the infrared absorption spectrometry, the reaction is carried out for 6 hours to 2250 (the absorption near 51^1 disappears, and further at a temperature of 98 ° C 2 The reaction was carried out in an hour to obtain 60% by weight of a soluble aqueous urethane resin containing an aqueous solution. The lipid solution was measured to obtain an acid value of 28.9 mgKOH/g (solid content acid value: 48.1 mgKOH/g). (A-4) Resin corresponding to the above carboxyl group-containing resin (7): Corresponding to the aforementioned carboxyl group-containing resin (7) A resin containing a photosensitive carboxyl group containing a polyfunctional epoxy group having a photosensitive biphenyl aldehyde varnish structure (manufactured by Nippon Kayaku Co., Ltd., 2 〇 & - 16011 £ (solid content: 65%, as a resin) The acid value was 98 mgKOH/g)]. Preparation of aluminum hydroxide slurry: 700 g of aluminum hydroxide (HIGILITEUM manufactured by Showa Denko Co., Ltd.), 280 g of ethyl diglycol acetate as a solvent, and BYK-1 10 of 20 g were mixed and stirred under the bead honing. The .5 μηη zirconia beads were subjected to dispersion treatment. This was repeated three times and then passed through a 3 μηι filter to prepare an aluminum hydroxide slurry (C-1). Examples 1 to 14 and Comparative Examples 1 to 3 to 51 - 201105742 Using the resin solutions of the respective synthesis examples described above, the addition table was used. ! The various components shown in the above and the ratios (mass parts) shown in Table 1 were prepared by mixing with a stirrer, and kneaded by three rolls to prepare a photosensitive resin composition for a solder resist. In addition, the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a double-scale precision fineness meter manufactured by Erichsen Co., Ltd., and was 15 μm or less. -52- 201105742 [Table 1] Composition Examples Comparative Example (parts by mass) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 2 3 Varnish 1 186 93 186 A component varnish 2 200 150 200 200 200 200 200 200 200 200 200 200 varnish 3 186 186 varnish 4 39 77 B component CR97” 50 50 50 50 50 50 50 50 50 50 50 50 50 50 C component C-1·2 80 50 50 50 50 50 50 50 50 50 50 50 50 50 80 50 D component NC-3000HCA70*5 50 50 50 50 50 50 50 50 45 45 50 50 50 50 50 50 50 FP-300·4 30 20 20 20 15 15 20 20 20 20 20 20 25 10 30 20 20 E Ingredients HFA-6065E, S 40 40 40 60 60 40 40 40 40 40 40 40 30 20 20 ExolitOP935** 5 10 ΤΡΟ'7 10 10 10 15 10 10 10 10 10 10 10 10 10 10 ΗComponent CGI-325·8 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 OXE-02'9 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2 0.5 0.5 ΝΠ-83Γ10 0.5 0.8 G composition DPCA60·'1 20 20 20 10 10 20 20 20 20 20 20 20 20 20 20 Melamine 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 DHT-4A'12 10 10 10 10 10 ΒΥΚ-110·13 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 0.5 0.5 0.5 0.5 carbitol acetate polyfluorene defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Indigo Blue 0.6 0.6 0.5 0.6 0.6 Pigment·Μ 0.15 0.15 0.2 Pigment·15 1.2 1.2 1.2 Pigment.16 0.1 IRGANOX1010*17 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 0.5 0.5 0.5 0.5 0.5 ΤΡΑ -Β80Ε*'8 5 5 Cellulose varnish ~ 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Hydrogenthiobenzothiazole 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 0.5 0.5 0.5 0.5 0.5

Shiyuan Industry. (Stock) Titanium Dioxide BS and Electrician (Share) Aluminum Mud Pulp Chemicals (Shares) Phenolic Aldehyde Epoxy Resin Carbitol Acetate Solution (Solid Content 70%) Phosphorus-containing compound made by Fushimi Pharmaceutical Co., Ltd. Phosphorus-containing compound modified polyester acrylate product, phosphorus compound, BASF, sulfhydryl phosphide oxide photopolymerization initiator, Luciferin TPO: Ciba specialty chemicals Company Brewing Photopolymerization Starter: Ciba specia丨ty chemicals Company vinegar photopolymerization initiator (share) ADEKA company photopolymerization initiator STARTEKARKLSNCI-831 Japan bismuth (stock) dipentaerythritol lactone Hydmta丨cite compound made by denatured hexaacrylate Concord Chemical Industry Co., Ltd. BYK Japan wet dispersion dispersant CIPigment red 264 CIPigment yellow 147 CIPigment black 1 Ciba specia丨ty chemicals Company Radical supplements Asahi Kasei Chemicals (Stock) company block isocyanate EASTMAN company CAB-553-0.4 (including ethyl ketone group: 2.0% ' containing butyl group: 46.0%, containing Xiangji: 4.8% · Tg : 136 ° C, M.W_20000) 30 wt% DPM solution _ -53-201105742 Performance evaluation: <Optimum exposure amount> The thermosetting/photocurable resin of the above Examples 2 to 14 and Comparative Examples 2 and 3 The composition was completely applied by a screen printing method to a circuit pattern substrate having a copper thickness of 35 μm after being honed by a polishing roll, washed with water, and dried, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, the exposure apparatus (HMW-680-GW20 manufactured by Oak Co., Ltd.) carried by a methyl halide lamp was exposed to a ladder plate (Kodak Νο. 2) for 90 seconds (30 ° C, The pattern of the ladder plate remaining after the 0.2 MPa, 1 wt% Na2CO3 aqueous solution) was used as the optimum exposure amount in the sixth stage. Characteristic test: The compositions of the above Examples 1 to 14 and Comparative Examples 1 to 3 were completely coated by screen printing on a polyimine film substrate having a pattern, and subjected to 30 minutes at 80 ° C. Dry and cool to room temperature. In the thermosetting resin compositions of Example 1 and Comparative Example 1, the obtained substrate was cured by heating at 150 ° C' for 60 minutes. The photocurable resin compositions of Examples 2 to 14 and Comparative Examples 2 and 3 were subjected to an exposure apparatus (HMW-680-GW20) carried by a methyl halide lamp on the obtained substrate, and were subjected to an optimum exposure amount. The exposure of the flux pattern was carried out by developing an aqueous solution of 1 wt% Na2C03 at 30 ° C for 90 seconds under a spray pressure of 0.2 MP a to obtain a photoresist pattern. The substrate was heated and cured at 150 ° C for 60 minutes. For the obtained printing substrate (evaluation substrate), the following characteristics were evaluated. -54-201105742 <Circuit concealability> The substrate obtained as described above was further heated at 1 40 ° C for 1 hour. The color of the copper circuit of the portion covered with the solder resist was confirmed to be discolored by heating at 140 ° C for 1 hour. 〇: Discoloration of copper-free circuit X: Confirmation of discoloration of copper circuit <soft soldering heat resistance> The evaluation substrate coated with rosin-based flux is immersed in a soldering groove set at 2 60 °C in advance. After the flask was washed with denatured alcohol, the expansion and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows. 〇: No peeling was confirmed under one 10 second immersion: no peeling was confirmed under one 5 second immersion: expansion and peeling of the photoresist layer under one 5 second immersion <low bending The hardened film prepared by Kaptonl OOH (Toray DuPont film, thickness 25 μm) was cut out 50×50 mm, and the 4-angle bending was measured, and the average enthalpy was determined, and the evaluation was performed on the following basis. 〇: When the bending is less than 1 mm, Δ: the bending is 1 mm or more, the thickness is less than 4 mm, and the bending is 4 mm or more. <Resolving property> -55, 201105742 Examples 2 to 14 and Comparative Example 2 The photosensitive resin composition of 3 was applied to the copper-clad substrate by screen printing, and dried at 80 ° C for 30 minutes. A negative film of L/S (line/pitch) = 1 00/5 00 μm was used, and exposure was performed at an optimum exposure amount, and development was carried out under the above conditions. After the development, confirm whether the line of ΙΟΟμηι remains. 〇: The line of ΙΟΟμιη remains on the copper substrate. X: There is no line of ΙΟΟμιη remaining on the copper substrate. <flammability> The composition of each of the examples and the comparative examples was subjected to full-coating by screen printing on a polytheneimide film (Kapton 50H, 100 Å manufactured by Toray DuPont) having a thickness of 12.5 μm or 25 μm. After drying at 80 ° C for 20 minutes, it was cooled to room temperature. Further, the film was completely coated by screen printing in the same manner, dried at 80 ° C for 20 minutes, and then cooled to room temperature to obtain a double-coated substrate. The thermosetting resin composition of Example 1 and Comparative Example 1 was obtained by heating the obtained double-coated substrate at 150 ° C for 60 minutes to be cured. For the photocurable resin compositions of Examples 2 to 14 and Comparative Examples 2 and 3, an exposure apparatus (11) ^·^-6 8 0 -GW20), the full exposure of the solder resist was performed at an optimum exposure amount, and a 1 wt% Na2CO3 aqueous solution at 30 ° C was developed under a spray pressure of 0.2 MPa for 90 seconds. Thermal hardening was carried out at 150 ° C for 60 minutes as an evaluation sample. For the sample for evaluation of flame retardancy, a vertical vertical burning test based on the UL94 standard was carried out. The evaluation is expressed as VTM-0 or VTM-1 according to the UL94 specification. The results of the above evaluation tests are summarized in Table 2 and Table 3. -56 - 201105742 [Table 2] Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Color blue, white, white, white, green, red, orange, purple, white, white and white exposure (mJ/cm2) 400 350 500 800 300 400 400 400 400 400 350 300 400 from concealed 〇〇〇〇〇〇〇0 〇〇〇〇〇〇 soldering heat resistance Δ 〇〇〇〇〇〇〇〇〇〇〇〇〇 low bending 〇〇〇 〇△ 〇〇〇〇〇〇〇〇〇resolution - 〇〇〇〇〇〇〇〇〇〇〇〇〇Kapton VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM4 VTM-0 VTM-0 VIM-0 VTM-0 VTM-0 Flame retardant 100H Pretty quite quite pretty quite quite pretty quite pretty quite pretty Kapton 50H legs dirty vm-o Pretty VTM-0 pretty legs Surface mm tm mm Female burning combustion VTM-0 is equivalent to VTM-0 equivalent [Table 3] Characteristic comparison example 1 2 3 color blue white green optimum exposure amount (mJ/cm2) 300 250 circuit concealing X 〇X soldering heat resistance △ 〇Δ low bending 〇〇X resolution - X 〇 flame retardant Kapton 10 0H Combustion combustion combustion Kapton 50H Combustion combustion combustion Example 1 5, 1 6 The composition shown in Examples 3 and 14 shown in Table 1 was prepared by adding a polysulfonium-based antifoaming agent to a curable resin composition. It was diluted with methyl ethyl ketone [S ] -57 - 201105742, coated on a supporting film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm, and a cover film was attached thereon to obtain a dry film. Thereafter, the cover film was peeled off, and a copper foil substrate having a pattern was formed, and a film was bonded using a laminate to prepare a test substrate. The evaluation test of each characteristic was carried out in the same manner as the above test method and evaluation method. The results are shown in Table 4. [Table 4] Characteristic Example 15 16-color white optimum exposure amount (m〗/cm2) 300 350 Circuit concealability 〇〇 Soldering heat resistance 〇〇 Low bending property 〇〇 Resolution 〇〇 Flame retardant Kapton 100H VTM- 0 Pretty VTM-0 Pretty Kapton 50H VTM-0 Pretty VTM-0 Pretty -58-

Claims (1)

201105742 VII. Patent application scope: 1. A curable resin composition characterized by containing (A) a resin containing a residue, (B) titanium oxide, and (C) aluminum hydroxide. 2. The curable resin composition according to claim 1, further comprising (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, further comprising (E) a phosphorus-containing compound. 4. The curable resin composition of claim 1, further comprising (F) a photopolymerization initiator and (G) a photopolymerizable monomer. 5. The curable resin composition according to claim 1, wherein the coloring agent (H) other than the titanium oxide (B) is contained. 6. The curable resin composition according to claim 1, wherein the sulfhydryl group-containing resin (A) is a carboxyl group-containing resin having a urethane skeleton. 7. The curable resin composition according to claim 1, wherein the residue-containing resin (A) has a biphenol novolak structure and an ethylenically unsaturated group. 8. 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 is a diphenol aldehyde. Epoxy resin enamel of varnish skeleton 9. The curable resin composition of the first to eighth aspects of the patent application is a solder resist. -59-201105742 10 - A dry film characterized by coating and drying a curable resin composition according to items 1 to 8 of the patent application range. 11. A cured product characterized by thermosetting and/or photohardening a dry coating film which is a curable resin composition according to items 1 to 8 of the patent application scope. The dried coating film obtained by drying and drying the substrate or the dry coating film obtained by coating and drying the curable resin composition on the film onto the substrate is laminated. 1 2. A printed circuit board characterized by having a cured product as in claim 1 of the patent application. -60- 201105742 IV Designated representative map: (1) The representative representative of the case is: None. (2) Simple description of the symbol of the representative figure: None 201105742 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none