TW200910006A - Photocuring resin composition, dry film, curing product and print circuit board - Google Patents

Abstract

The invention provides a photocurable resin composition, dry film, cured substance and printed circuit board. The invention provides a photocurable resin composition which is fully coloured, has high photosensitivity under the exposure of ultraviolet ray and laser such that it has good curing depth, in the mean time, adjusting absorption in the ultraviolet region by using red or yellow colorant as well as oxime ester initiators. The photocurable resin composition which may develop through alkaline aqueous solution contains (A) carboxylic acid-containing resins, (B) red colorants, (C) oxime ester initiators and (D) compounds having more than two unsaturated alkene groups in the molecules.

Description

200910006 IX. Description of the Invention [Technical Field] The present invention relates to a photocurable resin composition which can be developed with an aqueous alkali solution, in particular, a composition for solder resist resist which is exposed to ultraviolet light or laser, a dry film thereof, Hardened material, and printed wiring board. [Prior Art] Generally, a solder resist photoresist is formed to protect a copper circuit. On the other hand, there is also a discoloration, an electrochromic effect, a flaw in the copper circuit, and the like which are caused by the heat or moisture of the copper circuit. The solder resist is applied to a glass epoxy substrate formed of a copper circuit, and an image is formed by exposure, and the film pattern is formed by development and heat curing. Since a copper circuit is formed on the substrate, when the solder resist is coated or laminated thereon, the thickness of the photoresist film is thick on the substrate, but is thin on the copper circuit at the edge of the copper circuit. The part is even thinner. As a result, when the edge portion of the circuit in which the copper circuit is easily thinned is insufficient in coloring power, the copper is discolored in the heat history after the solder resist is formed, and the appearance of the thin portion is discolored. In this regard, in the past, a plurality of colorants were blended in the solder resist to improve the coloring power to solve the problem of seeing only the edge portion of the copper circuit is discolored. However, when many coloring agents are blended, other problems as described below are found at the time of exposure. That is, a general solder resist is colored green and blue, and a phthalocyanine compound having excellent heat resistance or chemical resistance is used as a coloring agent (refer to -4-200910006 Patent Document 1). However, the phthalocyanine compound is highly absorbed in the ultraviolet field and has an unfavorable problem in obtaining a depth of hardening. Further, the commercially available ultraviolet exposure apparatus has a difference in ultraviolet wavelength distribution depending on a lamp. Therefore, the phthalocyanine compound having a large absorption change in the ultraviolet field (especially from 35 nm to 400 nm) has difficulty in developing a solder resist having the same resolution with different exposure devices (lamps). On the other hand, from the viewpoint of the accuracy of the mating position, laser scanning exposure is common in exposure to solder resist. This laser exposure requires high resolution and a high resolution and good shape of the resist profile. Moreover, the laser exposure is different from the exposure of the ultraviolet lamp, and the light of a single wavelength is used. Therefore, the absorption of the light of the photoresist is important for the wavelength thereof, and the light of the light source used is a photopolymerization initiator. Effectively absorbed to determine sensitivity. Therefore, the presence of a light absorbing agent such as a coloring agent is not only unfavorable for high sensitivity, but also hinders the transmission of light to the bottom, causing an undercut problem. As described above, in order to cover the discoloration of the edge portion of the copper circuit, the phthalocyanine compound having a large light absorption in the ultraviolet field is used to obtain a sufficient coloring power, but the desired depth of hardening cannot be obtained, and undercut is generated. In order to prevent such a situation, the amount of the photopolymerization initiator is decreased, and the exposure cannot be performed with high sensitivity. On the other hand, in the case where the amount of the phthalocyanine compound is adjusted without undercutting and the concentration of the photopolymerization initiator is increased, the light sensitivity can be sufficiently obtained, but the edge of the copper circuit cannot be masked due to insufficient tinting strength. Part of the discoloration. -5-200910006 [Patent Document 1] JP-A-2000-7974, the scope of the patent application [Disclosure] [The problem to be solved by the invention] Therefore, the present invention provides a sufficient coloring while adjusting the absorption in the ultraviolet field. For the purpose of high-sensitivity and high-hardening composition in ultraviolet and laser exposure. Further, another object of the present invention is to provide a composition having high sensitivity and good hardening depth, which is further characterized by further adding a blue colorant or a green colorant to the above composition to change the photoresist toward green or blue. In the past, a small amount of addition has a sufficient coloring power for suppressing the appearance of discoloration or the like of a copper circuit. [Means for Solving the Problem] In order to achieve the object, the present invention has the following constitution. (1) A photocurable resin composition which can be developed with an aqueous alkali solution, comprising (A) a carboxylic acid-containing resin, (B1) a red colorant, and (C) an oxime ester-based photopolymerization initiator; D) A compound having two or more ethylenically unsaturated groups in the molecule. (2) A photocurable resin composition which can be developed with an aqueous alkali solution, comprising (A) a carboxylic acid-containing resin, (B2) a yellow colorant, and (C) an oxime ester-based photopolymerization initiator; (D) A compound having two or more ethylenically unsaturated groups in the molecule. (3) A photocurable tree -6-200910006 which can be developed with an aqueous alkali solution as described in (1), which has a fat composition selected from the group consisting of a yellow coloring agent (B2) and a blue coloring agent (B3). One or two. (4) The photocurable resin composition according to any one of (1) to (3), wherein the oxime ester photopolymerization initiator (C) is represented by the following general formula (I) An oxime ester photopolymerization initiator, which further comprises an α-aminoacetophenone photopolymerization initiator represented by the following general formula (II) and a mercaptophosphine represented by the following general formula (III) One or two kinds of oxide photopolymerization initiators, [Chem. 6] - C = N - 0 - C - R2

II R1 Ο (wherein R1 is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (may be 1) The above hydroxyl group may be substituted, and the alkyl chain may have one or more oxygen atoms in the middle thereof, a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having a carbon number of 2 to 20 or a benzoquinone group (which may be a compound having a carbon number of 1 to 6 or a phenyl group), R2 is a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), and a carbon number of 1 to 2 Å. a group (which may be substituted by one or more meridians) may have one or more oxygen-deficient atoms in the middle of the alkyl chain, a cycloalkyl group having a carbon number of 5 to 8, or a fluorenyl group having a carbon number of 2 to 20 or a phenyl fluorenyl group. (It can be replaced by the yard number or the base of the carbon number 1~6)) 200910006 [化7]

(ID (wherein R3 and R4 are independently alkyl or aralkyl groups having 1 to 12 carbon atoms, and R5 and R6 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or 2 Bonding to form a cyclic alkyl ether group)

(III) (wherein R7 and R8 are each independently a linear or branched group of a carbon number of 1 to 10, a cyclohexyl group, a cyclopentyl group, an aryl group, an alkoxy group, or a halogen atom. An aryl group substituted by an alkyl group or an alkoxy group, wherein R7 and R8 are R-C(=0)-group (wherein r may be a hydrocarbon group having 1 to 20 carbon atoms)). (5) The photocurable resin composition according to the above formula (I), wherein the oxime ester photopolymerization initiator (C) represented by the above formula (I) is an oxime ester represented by the following formula (IV) Photopolymerization initiator, -8- 200910006

(6) The photocurable resin composition of the above formula (I), wherein the oxime ester photopolymerization initiator (C) represented by the general formula (I) is represented by the following general formula (V). Ester photopolymerization initiator, [10]

(V) (wherein R9 is a hydrogen atom, a halogen atom, a carbon number of 1 to 12, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoinyl group, and a carbon number of 2 to 12;院 羯 2 碳 碳 ( ( ( ( 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳Oxygen atom), or phenoxycarbonyl, RIO, R12 are each independently phenyl (can be substituted by a carbon number of 1 to 6, -9 - 200910006 phenyl or halogen atom), carbon number 1~20 An alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkyl fluorenyl group having 2 to 20 carbon atoms or a benzoinyl group (It can be replaced by a hospital base or a phenyl group having a carbon number of 1 to 6),

Rii is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted by i or more hydroxyl groups, and an alkyl chain) Having at least one oxygen atom in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a phenylhydrazine group (which may be an alkyl group or a phenyl group having 1 to 6 carbon atoms) Replace)). (7) The photocurable resin composition according to any one of (1) to (6), wherein the enamel contains (E) a thermosetting component. (8) The photocurable resin composition according to any one of (1) to (7) wherein the composition is an anti-set having a color tone selected from the group consisting of blue, green, orange, and purple. Solder resist. (9) A photocurable dry film obtained by applying the photocurable resin composition according to any one of (1) to (8) to a carrier film and drying the film. (1 〇) A cured product obtained by photocuring the photocurable resin composition according to any one of (1) to (8) or the dry film described in (9) on copper. (1 1 ) A cured product of the photocurable resin composition according to any one of (1) to (8) or the dry film of (9), which is obtained by photohardening. (1) A printed wiring board characterized in that the photocurable resin composition according to any one of (10) to (10), or the dry film described in (9) is photohardened. After that, it is obtained by heat hardening. (1 3 ) A printed wiring board having an insulating layer characterized by containing a red coloring agent (B 1 ). (Definition of the composition and the color of the solder resist) The color of the composition and the solder resist is based on the color hue ring of JISZ8 72 1 and the Munsell hue ring (Japan Color Research Institute) The symbol indicated by the supervision of the new basic color chart series 2 issued by Munsell Systems Japan Color Equipment Co., Ltd. can be distinguished (refer to the Munsell Hue Ring Chart 1). Red 7RP to less than 9R range Orange 9R to less than 7YR range Yellow 7YR to less than 9Y range Green 9Y to less than 5BG range Blue 5BG to less than 3P range Purple 3P to less than 7RP range The brightness and chroma are different depending on the underlying layer (glass epoxy substrate or copper circuit and surface treated copper circuit), and the chroma is 1 or more and less than 16, and the brightness is 1 or more and less than 9'. The chroma is 2 or more and less than 15, and the height is 2 or more and less than 9 (brightness and chroma are based on JISZ8 1 02 JISZ872 1). Further, the suitable measurement conditions are based on a solder resist having a thickness of 2 Å to 3 Å μm and preferably on a copper circuit. -11 - 200910006 In the present invention, the printed wiring board is formed by using a printing technique such as a screen printing method or a light etching method on the surface of the electrically insulating substrate to form a conductor pattern substrate having rigidity. Wiring board and flexible wiring board. [Effect of the Invention] In the present invention, it is possible to provide a composition which is capable of adjusting the absorption in the ultraviolet field and having sufficient coloration by using a red or yellow coloring agent and an oxime ester photopolymerization initiator, in ultraviolet light and In the laser exposure, it is a composition with high sensitivity and good hardening depth. Further, a blue coloring agent or a green coloring agent is added to the composition to change the photoresist to green or blue, and the coloring resistance is sufficient to suppress the appearance of discoloration such as discoloration of the copper circuit. A composition with high sensitivity and good hardening depth is provided. [Best Mode for Carrying Out the Invention] Hereinafter, each constituent component of the photocurable resin composition of the present invention will be described in detail. (A) Resin containing a carboxylic acid The resin (A) containing a carboxylic acid contained in the photocurable resin composition of the present invention may be a resin compound known in the art and containing a carboxylic acid. Further, the carboxylic acid-containing photosensitive resin (A ') having an ethylenically unsaturated double bond in the molecule is preferably in terms of photocurability or developability. -12- 200910006 Specifically, a resin exemplified below can be cited. (1) to (9) and the like: (1) A carboxylic acid-containing copolymer resin obtained by using an unsaturated carboxylic acid such as (meth)acrylic acid or the like (2) A photosensitive resin containing a carboxylic acid, which has an unsaturated carboxylic acid such as (meth)acrylic acid, and one or more other unsaturated ones, which are obtained by copolymerization of a compound having an unsaturated double bond. a copolymer of a compound of a double bond, a compound having an epoxy group having an glycidyl group (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate and an unsaturated double bond Or (meth)acrylic acid chloride or the like, which is obtained by adding an ethylenically unsaturated group as a pendant, and (3) a photosensitive carboxylic acid-containing copolymer resin, which is a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having another unsaturated double bond Copolymer, in the form of (meth)acrylic acid, etc. And the generated secondary hydroxyl group is obtained by reacting a polybasic acid anhydride, and (4) a photosensitive resin containing a carboxylic acid, which is an acid anhydride having an unsaturated double bond such as maleic anhydride, and the like A copolymer of a compound having an unsaturated double bond is obtained by reacting a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with an unsaturated double bond, and (5) a photosensitive property containing a carboxylic acid. a resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting the generated hydroxyl group with a saturated or -13 - 200910006 unsaturated polybasic acid anhydride, (6) containing a hydroxyl group and a carboxylic acid A photosensitive resin obtained by reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride to form a carboxylic acid having an epoxy group and an unsaturated double bond in one molecule. According to the reaction, (7) a photosensitive resin containing a carboxylic acid, which is an alcohol having a polyfunctional epoxy compound 'unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule and an epoxy group One reaction other than a hydroxyl group The reaction product of the compound of the group is determined by a reaction of a saturated or unsaturated polybasic acid anhydride, and (8) a photosensitive resin containing a carboxylic acid, which has at least two oxetane rings in one molecule. a functional oxetane compound, which is obtained by reacting an unsaturated monocarboxylic acid and reacting a first-order hydroxyl group in the obtained modified oxetane resin with a saturated or unsaturated polybasic acid anhydride, and (9) A photosensitive resin containing a carboxylic acid, which is a carboxylic acid-containing resin obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid, and then reacting a polybasic acid anhydride, and further having one ethylene oxide in the molecule ( The oxirane) ring is obtained by reacting a compound having one or more ethylenically unsaturated groups, but is not limited thereto. In the above examples, the carboxylic acid-containing resin of the above (2), (5), and (7) is preferable, and the carboxylic acid-containing photosensitive resin of the above (9) is preferably photocurable or cured. In terms of surface, it is preferred. Further, in the present specification, the terms "(meth)acrylate" collectively referred to as acrylate, methacrylate and a mixture thereof are the same as in other similar expressions. -14- 200910006 The carboxylic acid-containing resin (A) as described above is developed by a large amount of free hydrazine in the side chain of the backbone polymer. Further, when the acid cerium of the carboxylic acid-containing resin (A) is in the range of 40 to KOH/g, preferably 45 to 120 mgKOH/g, the acid cerium of the carboxylic acid resin is less than 40 mgKOH/g, alkali development On the other hand, when it exceeds 200 mgKOH/g, it is necessary to make the line thinner by the dissolution of the developing solution portion, and there is a case where the portion and the unexposed portion are not easily dissolved and peeled off in the developing solution, and the normal photoresist is formed. The drawing becomes difficult, so it is not good. Further, the weight average of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, but is generally 2, preferably in the range of 〇〇〇1 to 150,000 and 5,000 to 100,000. Weight average molecular weight: 2,000 hours, poor adhesion performance, moisture resistance of the film after exposure, film reduction during development, and poor resolution. On the other hand, when the weight average is more than 1,500,000, the developability is remarkably deteriorated, and the storage stability is formed. The blending amount of the carboxylic acid-containing resin (A) is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass. When the range is small, the coating film strength is lowered, which is not preferable. On the other hand, in the case where there are many ranges, the viscosity is high and the coating property is lowered, so that the colorant can be used as a pigment dye, a dye, or a polymerizable base. 0 mg circumference. In the case of difficulties, the exposure is not subject to the sub-quantity of the pattern, and the composition is poor in molecular weight and poor in molecular weight. Compared with any one of the above -15-200910006. Specifically, the following can be used. (B 1 ) Red colorant as a red colorant' has a monoazo system, a disazo system, an azo lake system, a benzoquinone series, an anthraquinone, a diketopyrrolopyrrole (diketopyrrolopyrrole) The system is a condensed azo system, a brewing system, a quinacridone, or the like. Specifically, the following coloring K can be exemplified. (monoazo)

Pigment Red 1,2,3,4,5,6,8, 9,12,14,15,16,17,21,22,23,31,32,112,114,1 46, 147,151,170 ,184,1 87, 1 8 8, 1 93, 210,245, 253, 25 8, 266, 267,268,269, (double azo)

Pigment Red 3 7, 3 8,41 (monoazolake)

Pigment Red 48:1,48:2,48:3, 48:4, 49:1,49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4,63:1, 63:2, 64:1, 68 (benzimidazolone)

Pigment Red 171, Pigment Red 175, Pigment Red 176, -16- 200910006

Pigment Red 185, Pigment Red 208 (茈)

Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 (dione-based pyridinium and pyridinium) Pigment Red 2 5 4, Pigment Red 2 5 5, Pigment Red 264, Pigment Red 270, P i gment Red 2 72 (condensed azo) Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 2 14, Pigment Red 220, Pigment Red 22 1, Pigment Red 242 (Planting System) Pigment Red 168, Pigment Red 177, Pigment Red 2 16, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 (Quinacridone) Pigment Red 1 22, Pigment Red 202, Pigment Red 206, -17- 200910006

Pigment Red 207, Pigment Red 209. Among these red colorants, it is suitable in particular in the ultraviolet field and the absorption change from 350 to 400 nm is small. Further, a coloring agent other than a nitrogen-based compound and a non-halogen compound are preferable in terms of hydrazine. A suitable red coloring agent is exemplified by the blending amount of Pigment Red Pigment Red 264 crimson coloring agent, and the ultraviolet ray 5 is 100 parts by mass of the carboxylic acid-containing resin (A). It is preferably 0.05 to 3.0 parts by mass. (B2) Yellow coloring agent The yellow coloring agent may be a monoazo type, a bisazo type, a box type, a benzimidazolone type, an isoindane type, an anthraquinone type, or the like, and has the following coloring agents. (蒽醌系)

Solvent Yellow 163, Pigment Yellow 24, Pigment 1 08, Pigment Yellow 193, Pigment Yellow 147, Yellow 199, Pigment Yellow 202 (Different)

Pigment Yellow 110, Pigment Yellow 109, Pigment 139, Pigment Yellow 179, Pigment Yellow 185 Small collection, with occasional pollution 177, yield '-5.0 azo azo

Yellow Pigment

Yellow 18_ 200910006 (condensed azo)

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180 (benzimidazolone)

Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 (single azo) P igment Y e 11 ow 1,2,3,4,5,6,9,10, 12, 61, 62? 62:1, 65, 73, 74,75,97,100,104,105,111,116,167,168,169, 182, 183, (bisazo)

Pigment Yellow 12, 13,14,16, 1 7,5 5,6 3,8 1,8 3,8 7,126, 127,152,170,172,174,176,188,198 These yellow colorants Among them, it is suitable for the small absorption in the ultraviolet field and the small change in absorption from 350 to 400 nm. Further, a coloring agent other than the azo compound and a non-halogen compound are preferred in terms of environmental pollution. A more suitable yellow colorant' can be cited as Solvent YeUow 163, -19- 200910006

Pigment Yellow 24, Pigment Yellow 193, Pigment Yellow 193 ' Pigment Yellow 199 ' Pigment Yellow 202 ' Pigment Yellow 110 ' Pigment Yellow 109 ' Pigment Yellow 109 ' Pigment Yellow 139 , Pigment Yellow 179 , Pigment

Yellow 185, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 1 54 , Pigment Yellow 156 , Pigment

Yellow 175, Pigment Yellow 181, etc. The blending amount of the yellow coloring agent is from 0.01 to 5 parts by mass, preferably from 0.05 to 3 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (A), in consideration of the coloring property and the ultraviolet absorbing amount. (B 3 ) Blue colorant The blue colorant is blended so that the color tone of the composition becomes green, blue or orange. The blue colorant to be blended is a phthalocyanine-based or an anthraquinone-based, and the pigment is a compound classified as a pigment. Specifically, a color index (CI; The Society of Dyers) may be exemplified. And Colourists company issued) number. be usable

Pigment Blue 15 , Pigment Blue 15:1 , Pigment Blue 15:2 ' Pigment Blue 15:3 ' Pigment Blue 15:4 ' Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60 Dye

Solvent Blue 35, Solvent Blue 63, Solvent Blue 68 ' -20- 200910006

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. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above. Among these blue colorants, those which have a small absorption in the ultraviolet field and a small change in absorption from 350 to 400 nm are suitable. Suitable blue colorants include Pigment Blue 15, Pigment Blue 15:1 ' Pigment Blue 15:2 ' Pigment Blue 1 5 :3, Pigment Blue 15:4 ^ Pigment Blue 15:6, Pigment Blue 1 6, Pigment Blue 60 ' Solvent Blue 35 ' Solvent Blue 63 , Solvent Blue 68 ' Solvent Blue 7 0 ' Solvent Blue 83 , Solvent Blue 87 , Solvent Blue 94 , Solvent Blue 97 , Solvent Blue 122 , Solvent Blue 136 , Solvent Blue 67 , Solvent Blue 70 ^ o The blending amount of the blue coloring agent is a coloring property and an ultraviolet absorbing amount, and is 0.01 to 5 parts by mass, preferably 〇.〇5~, for 100 parts by mass of the carboxylic acid-containing resin (A). 3 parts by mass. The blending amount of the blue colorant mixed in the red colorant and the yellow colorant is such that the hue is green or blue, and the coloring property and the ultraviolet absorbing amount are considered to be 100 Å for the carboxylic acid-containing resin (A). The total amount of the coloring agent is 0.5 to 5 parts by mass, preferably 〇. 5 to 4 parts by mass. (Coloring agent of other color tone) The present invention is such that the color tone of the composition is green - blue or orange - 21 - 200910006, and green and purple other than the above may be added within a range not inhibiting the object of the present invention. A coloring agent such as orange, brown or black. The green coloring agent is a phthalocyanine system, specifically, Pi Gment Green 7, Pigment Green 3 6, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above. Other coloring agents other than green include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C_I. Pigment Orange 1, C. I · Pigment Orange 5, C. I · Pigment Orange 1 3, c. I. Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, C_I. Pigment Orange 24, CI Pigment Orange 34'CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, C.I_Pigment Orange 49, CI Pigment Orange 5 1, C.I_Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, and the like. (C) oxime ester-based photopolymerization initiator In the present invention, any oxime ester-based photopolymerization initiator can be used, and in particular, an oxime ester-based photopolymerization initiator having the group represented by the above general formula (I) is good. Further, 'the use of an α-aminoacetophenone photopolymerization initiator selected from the group represented by the above general formula (II) and a mercaptophosphine having the group represented by the above general formula (ΠI) A photopolymerization initiator which is a group of an oxide photopolymerization initiator is preferred. By using a photopolymerization initiator having a group represented by the general formula (11) or the general formula (III), the long-wavelength light -22 - 200910006 source has an effect of enlarging the photosensitive field. An oxime ester-based photopolymerization initiator having the group represented by the above general formula (I), which has the above formula (IV) 2-(ethylhydrazinylmethyl)thioxanthene-9-one, and has the above general The compound represented by the formula (V) is preferred. Commercially available products include CGI-325, IRGACURE OXEOl, and IRGACURE OXE02 manufactured by Ciba Specialty Chemicals. These oligoester photopolymerization initiators may be used alone or in combination of two or more. The α-aminoacetophenone photopolymerization initiator having the group represented by the above general formula (II), and 2-methyl-1-[4-(methylthio)phenyl]-2- Oleone acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[( 4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, anthracene, fluorenyl-dimethylaminoacetophenone and the like. Commercially available products include IRGACURE 907, IRGACURE 3 69, IRGACURE 3 79, and the like manufactured by Ciba Specialty Chemicals. The mercaptophosphine oxide-based photopolymerization initiator having the group represented by the above general formula (III) may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2, 4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide Wait. Commercially available products include Lucirin TPO manufactured by BASF Corporation and IRGACURE 819 manufactured by Ciba Specialty Chemicals. The amount of the photopolymerization initiator (C) to be blended is 100 parts by mass of the carboxylic acid-containing resin (A), and may be selected from the group consisting of 〇01 to 30 parts by mass, preferably 0. 5~ A range of 15 parts by mass. When the amount of the film is less than 0. 0 1 part by mass, the photocurability of the film is insufficient, and the film peeling property and the chemical resistance of the film are lowered, which is not preferable. On the other hand, when the amount exceeds 30 parts by mass, the light absorption on the surface of the solder resist film of the photopolymerization initiator (C) becomes intense, and the deep hardenability tends to be lowered, which is not preferable. Further, in the case of the oxime ester-based photopolymerization initiator having the group represented by the above general formula (I), the blending amount is preferably 100 parts by mass based on the carboxylic acid-containing resin (Α). It is preferably selected from the range of 1 to 20 parts by mass, more preferably 〇·0 1 to 5 parts by mass. (D) Compound having two or more ethylenically unsaturated groups in the molecule The compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is Photocuring is carried out by irradiation of an active energy ray, and the carboxylic acid-containing resin (A) is insolubilized in an aqueous alkali solution or helps to dissolve. Examples of such a compound include diacrylates of ethylene glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and ginseng; a polyhydric alcohol such as a hydroxyethyl isomeric cyanurate or a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; Polyacrylates such as acrylates, bisphenol A diacrylates, and such phenolic ethylene oxide adducts or propylene oxide adducts; a polyacrylate of a glycidyl ether such as glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl isocyanurate; and melamine acrylate, and/or corresponding Each of the above acrylates is -24-200910006 methacrylate or the like. Further, examples thereof include a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin reacted with acrylic acid, or a hydroxyl group of an epoxy acrylate resin, such as 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. Such an epoxy acrylate-based resin does not deteriorate the finger-drying property and can improve the photocurability. The blending amount of the compound (D) having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 part by mass to 100 parts by mass of the carboxylic acid-containing resin (A). ~70 parts by mass ratio. When the amount of the above-mentioned blending is less than 5 parts by mass, the photocurability is lowered, and the alkali development after the irradiation of the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, in the case of more than 100 parts by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable. When the above-mentioned mixture is used, one or more kinds of oxime ester-based photopolymerization initiators having a group represented by the general formula (I) and having a general formula are used for 100 parts by mass of the carboxylic acid-containing resin (A). Light of the group of the α-aminoacetophenone photopolymerization initiator represented by (Π) and the mercaptophosphine oxide photopolymerization initiator having a group represented by the general formula (III) The polymerization initiator is 1 to 15 parts by mass, preferably 3 to 1 part by mass. (Ε) Thermosetting component The photosensitive composition of the present invention is a heat-resistant one, and a thermosetting component can be added. Particularly preferred is a thermosetting component (E) having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter, abbreviated as a cyclic (thio)ether group) in the molecule. The thermosetting component (E) having two or more cyclic (thio)ether groups in such a molecule is a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a ring. Any one of the thioether groups or a compound of the two groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E 1 ); at least two or more in the molecule; An oxetanyl compound, that is, a polyfunctional oxetane compound (E2); a compound having two or more thioether groups in the molecule, that is, an episulfide resin (E3) )Wait. Examples of the polyfunctional epoxy compound (E1) include EPIKOTE 828, EPIKOTE 834, EPIKOTE 1001 'EPIKOTE 1004 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON 840, EPICLON 85 0, and EPICLON 1 050 manufactured by Dainippon Ink and Chemicals. EPICLON 205 5, EPOTOHTO YD-011, YD-013, YD-127, YD-128, manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664, Ciba, manufactured by Dow Chemical Company

Specialty Chemicals Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Chemical Industries, Inc. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER3 3 0 by Asahi Kasei Kogyo Co., Ltd. , AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; EPIKOTE YL903 manufactured by Japan Epoxy Resins Co., Ltd., Day -26- 200910006 EPICLON 152, EPICLON manufactured by Ink Chemical Industry Co., Ltd. 165, EPOTOHTO YDB-400, YDB-500 manufactured by Dongdu Chemical Co., Ltd. DER5 42' manufactured by Dow Chemical Co., Ltd. Araldite 801 manufactured by Ciba Specialty Chemicals Co., Ltd. Sumi-epoxy ESB-400, ESB- manufactured by Sumitomo Chemical Industries, Ltd. 700, brominated epoxy resin of AER711, AER714, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.; EPIKOTE 152, EPIKOTE 154 manufactured by Japan Epoxy Resins Co., Ltd., DEN431, DEN438, manufactured by Dow Chemical Co., Ltd., Japan EPICLON N-730, EPICLON N-7 70, EPICLON N-865 manufactured by Ink Chemical Industry Co., Ltd., EPOTOHTO YDCN-701, YD CN- manufactured by Dongdu Chemical Co., Ltd. 704, Araldite ECN 1 23 5 from Riba Specialty Chemicals, Araldite E CN 1 2 73 'Araldite ECN 1 299, Araldite XPY3 07, EPPN-201, EOCN-1025, EOCN-1020, EOCN- manufactured by Nippon Kayaku Co., Ltd. 104S, RE-3 06 > Sumi-epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, Inc., AER ECN-23 5, ECN-299, etc. (all trade names) made by Asahi Kasei Kogyo Co., Ltd. Oxygen resin; EPICLON 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPIKOTE 807 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTO YDF-170, YDF-175, YDF-2 004 manufactured by Dongdu Chemical Co., Ltd., Araldite XPY306 manufactured by Ciba Specialty Chemicals Bisphenol F type epoxy resin (both trade names); hydrogenated bisphenol A type epoxy resin such as EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; Japan Epoxy Resins EPIKOTE 604, manufactured by Dongdu Chemical Co., Ltd. -27- 200910006 ΕΡΟΤΟΗΤΟ ΥΗ-434 > Araldite MY72 0 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industries Glycidylamine type epoxy resin (all trade name); hydantoin type epoxy resin such as Araldite CY-3 5 0 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.; CELLOXIDE manufactured by DAICEL Chemical Industry Co., Ltd. 2021 , Ciba Specialty

An alicyclic epoxy resin of Araldite CY175, CY179, etc. (all trade names) manufactured by Chemicals Co., Ltd.; YL- 9 3 3 manufactured by Japan Epoxy Resins Co., Ltd., TEN, EPPN-501, EPPN-5 02 manufactured by Dow Chemical Co., Ltd., etc. Trihydroxyphenylmethane type epoxy resin (all trade names); biphenylphenol type or bisphenol type ring of YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Japan Epoxy Resins Co., Ltd. Oxygen resin or a mixture of them; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA_ 15 14 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd. ; bisphenol A lacquer-type epoxy resin such as EPIKOTE 15 7S (trade name) manufactured by Japan EP〇Xy Resins Co., Ltd.; EPIKOTE YL - 9 3 1,C ib a Spe ci alt y C manufactured by Japan Epoxy Resins Co., Ltd. Te phenolethane type epoxy resin of Araldite 163 (all trade name) manufactured by Hemic Co., Ltd.; Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEP 1C manufactured by Nissan Chemical Industries Co., Ltd. (all trade names) Ring epoxy resin; Japan Oil Company BLEMMER DGT, etc. diglycidyl phthalate resin; manufactured by Tohto Kasei Co. ZX- 1 063 tetraglycidyl like ethane-cresol (g Shu ycidyi xyienoy1 ethane) resin; Nippon Steel of -28-200910006

ESN-190, ESN-360, and Naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; HP-7200 manufactured by Dainippon Ink Chemical Industry Co., Ltd. An epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; a glycidyl methacrylate copolymerized epoxy resin such as CP-50S or CP-50M manufactured by Nippon Oil Co., Ltd.; and further cyclohexyl-n-butene Copolymerized epoxy resin of diimine and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resin ( For example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd., etc., but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable. The above polyfunctional oxetane compound (E2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-oxa) Cyclobutylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3- Oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, or oligomers thereof Polyfunctional oxetane such as copolymer, and other oxetane and novolak resins, poly(P-hydroxystyrene), cardo type type, a calixarene type, a calixarene (a calixresorcinarene) type, or an acid compound of a resin having a warp group such as a sesquifere -29-200910006 (silsesquioxane). Further, examples thereof include an unsaturated monomer having an oxetane ring and a copolymer of an alkyl group (methyl group), and a compound having two or more cyclic thioether groups in the molecule. (E3), for example, a bismuth a-type sulfide resin YL7000 manufactured by Japan Epoxy Resins Co., Ltd., etc. Further, by the same synthesis method, an epoxy atom of a novolac type epoxy resin may be used instead. The surface sulfide resin which is a sulfur atom. The blending amount of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is 1 equivalent to the carboxyl group of the carboxylic acid-containing resin. It is preferably in the range of 〜6 to 2.5 equivalents, more preferably in the range of 〇8 to 2.0 equivalents, and a blending amount of a thermosetting component (Ε) having two or more cyclic (thio)ether groups in the molecule. 'There is a residual carboxyl group in the solder resist film when it is less than 0.6' and the heat resistance, alkali resistance, electrical insulation, etc. are reduced. Therefore, it is not good. On the one hand, when it exceeds 2.5 eq, it is caused by a low molecular weight ring ( The thio)ether group remains on the dried coating film, and the strength of the coating film is lowered, which is not preferable. When a thermosetting component (Ε) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferable to contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole and 2-methyl group. Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl miso, 1-(2- Miso derivatives such as aminoethyl)-2-ethyl-4-methyl miso; dicyandiamide, benzylamine, 4-(dimethylamino)-N,N- Amine compound such as dimethyl amide, 4-methoxy-N,N-dimethyl benzylamine, 4-methyl-indole, hydrazine-dimethylbenzylamine; diammonium adipate-30- 200910006 An anthracene compound such as ruthenium or azelaic acid; a phosphorus compound such as triphenylphosphine; and a commercially available product such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Chemical Industry Co., Ltd. U-CAT3 503N, U-CAT3 502T (trade name of block isocyanate compound of dimethylamine) manufactured by SAN-APRO Co., Ltd., DBU, DBN, U-CATSA102, U-CAT5002 (trade name) All bicyclic guanidine compounds and their salts), etc. Alternatively, a thermosetting catalyst of an epoxy resin or an oxetane compound may be used, or a reaction which promotes the reaction of an epoxy group and/or an oxetanyl group with a carboxyl group, alone or in combination. It is also possible to use two or more kinds. It is also possible to use gu an amine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl. -S-three tillage, 2-vinyl-4,6-diamino-S-three tillage, 2-vinyl-4,6-diamino-S-triterpene-iso-cyanuric acid adduct And an S-triterpene derivative such as a 2,4-diamino-6-methylpropenyloxyethyl-S-triazine. an isomeric cyanuric acid addition product, preferably as a dense The functional imparting agent is also a functional compound and the aforementioned thermosetting catalyst. It is sufficient that the blending amount of the thermosetting catalyst is a ratio of a general amount, for example, 'for a carboxylic acid-containing resin (A) or a thermosetting component having two or more cyclic (thio)ether groups in the molecule. (E) 100 parts by mass, preferably 1-1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. Tilting agent The photocurable composition of the present invention is a blending agent which can be blended as needed to improve the physical strength of the coating film. As such a chelating agent, an inorganic or organic hydrazine used in the prior art -31 - 200910006 can be used, and barium sulfate, spheroidal cerium oxide and talc are particularly preferably used. Further, a compound having two or more ethylenically unsaturated groups in the molecule or NANOCRYL (trade name) XP 0396 manufactured by Hanse-Chemie Co., Ltd. in which the nano-sized cerium oxide is dispersed in the polyfunctional epoxy resin (E1) may be used. , XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade name) or HANNOPOX (trade name) manufactured by Hanse-Chemie Inc. XP 0516, XP 0525, XP 0314 (All product grade name). These may be used alone or in combination of two or more. The blending amount of the above-mentioned chelating agent is preferably 30,000 parts by mass or less, more preferably 〇1 to 30,000 parts by mass, particularly preferably 0.1% by mass based on 1 part by mass of the carboxylic acid-containing resin (A). ~150 parts by mass. When the blending amount of the chelating agent exceeds 300 parts by mass, the viscosity of the photocurable composition becomes high, the printability is lowered, and the hardening of the cured product is not preferable. Further, the photocurable resin composition of the present invention is an organic solvent which is used for the adjustment of the synthesis or composition of the carboxylic acid-containing resin (A) or the viscosity adjustment 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; cellosolve, methyl cellosolve, butyl cellosolve, and carbene Alcohol, methyl carbitol, butyl carbitol '-32- 200910006 propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Alcohol ethers; esters of ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, An alcohol such as ethylene glycol or propylene glycol; an aliphatic hydrocarbon such as octane or decane; or a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. Such an organic solvent may be used singly or in combination of two or more kinds. Other photosynthetic resin composition of the present invention may be blended with hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, etc., if necessary. Conventionally known thermal polymerization inhibitors; micro-powder ceria, organic bentonite, montmorillonite, etc., known as tackifiers, polyoxyalkylene systems, fluorine-based, polymer-based defoamers and/or Additives such as a flattening agent, a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, an antioxidant, and a rust preventive agent. Further, the present invention may blend a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenylketone compound, a xanthone, to the extent that the object of the present invention is not impaired. Other photopolymerization initiators, or photoinitiating aids and sensitizers represented by the compounds, and tertiary amine compounds. The photocurable resin composition of the present invention is preferably one having a green color or a blue color. Such a color tone can be suitably obtained by blending a single coloring agent or a mixture of a plurality of coloring agents -33-200910006. Dry film, cured product, and printed wiring board The photocurable resin composition of the present invention obtained in this manner is applied to a carrier film by a usual means and dried to obtain a photocurable dry film. The photocurable resin composition of the present invention or the dry film is obtained by photohardening on copper. The photohardening system can also be carried out by means of an ultraviolet exposure device which is hardened by, in particular, laser light having a wavelength of from 350 to 410 nm. The printed wiring board according to the present invention is obtained by photohardening in this manner and then thermally hardening. Specifically, a dry film, a cured product, and a printed wiring board can be formed as follows. In other words, the photocurable resin composition of the present invention is adjusted to have a viscosity suitable for the coating method, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or the like. Coating by a screen printing method, a curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (pseudo-drying) at a temperature of about 60 to 100 ° C to form a tack-free. Coating film. Further, the above composition is applied onto a carrier film, and the resin insulating layer is formed by being wound and bonded to a substrate by drying it into a film type. Thereafter, by contact (or non-contact), through the formation of the pattern of the mask, selective exposure by active energy lines or direct exposure by laser direct exposure machine, but not The exposed portion is developed by an aqueous alkali solution (for example, 0.3 to 3% aqueous alkali carbonate solution) to form a photoresist pattern. Further, in the case of the composition containing the thermosetting component (E), in the case of -34 to 200910006, for example, heating at a temperature of about 1 40 to 180 ° C, the carboxylic acid-containing resin (A) is obtained by thermally hardening it. The carboxyl group reacts with the thermosetting component (E) having two or more cyclic ether groups and/or a cyclic thioether group in the molecule to form heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. A cured coating film having excellent properties such as properties. In addition, even if the thermosetting component (E) is not contained, the ethylenic unsaturated bond remaining in the unreacted state during the exposure is thermally polymerized by heat treatment, and the coating film characteristics can be improved. Purpose • Use for heat treatment (thermal hardening). The above substrate is made of paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine, polyethylene, PPO. - a high-voltage circuit such as a cyanate ester, etc., such as a copper-clad laminate or the like, and a copper-clad laminate of (FR-4 or the like), and other examples thereof include a polyimide film. PET film, glass substrate, ceramic substrate, wafer board, and the like. After the photocurable resin composition of the present invention is applied and volatilized and dried, a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (using a heat source heated by steam and dried) can be used. The method of contacting the hot air in the machine and the method of spraying the nozzle toward the support is performed. The photocurable resin composition of the present invention is applied as follows, and after the evaporation and drying, the obtained coating film is exposed (irradiated active energy ray). The coating film exposure portion (the portion irradiated by the active energy ray) is hardened. -35- 200910006 The exposure machine used for the above-mentioned active energy ray can be used with a laser direct drawing device (Laser direct imaging device), an exposure machine equipped with a metal halide lamp, and equipped with (ultra) high voltage. An exposure device for a mercury lamp, an exposure device equipped with a mercury short-arc lamp, or a direct drawing device for an ultraviolet lamp such as an (ultra) high-pressure mercury lamp. The active energy ray may be either a gas laser or a solid laser if it uses laser light having a maximum wavelength in the range of 305 to 4 10 nm. Further, the exposure amount varies depending on the film thickness and the like, and is usually in the range of 5 to 200 mJ/cm 2 , preferably 5 to 100 mJ/cm 2 , more preferably 5 to 50 mJ/cm 2 . As the direct drawing device, for example, a product manufactured by Orbotech Co., Ltd., PENTAX Corporation, or the like, and a device having a maximum wavelength of laser light of 350 to 410 nm can be used, and any device can be used. The developing method may be a dipping method, a shower method, a spray method, a brushing method, or the like; as the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or an amine may be used. An aqueous solution such as an alkali. [Embodiment] The following examples and comparative examples are specifically described in the present invention, and the present invention is not limited to the following examples. Resin Synthesis Example 1 A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point) was introduced into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube. 92 ° C, epoxy when -36 - 200910006 amount 220) 660g, carbitol acetate 421.3g and solvent naphtha 18 0.6g 'heated at 90 ° C. Stir and dissolve. Then, 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methyl hydroquinone were added to the mixture at a temperature of 60 ° C., and the mixture was reacted for 12 hours in a loot to obtain a reaction product of acid oxime of 0.2 mgKOH/g. Here, tetrahydrophthalic anhydride 2 4 1 .7 g ' was added and heated at 90 ° C to carry out a reaction for 6 hours. Thus, a solution of a carboxylic acid-containing resin (A) having a weight of 50 mg KOH/g, a double bond equivalent (g weight per 1 mole of the unsaturated group resin) 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, the solution containing the carboxylic acid-containing resin is referred to as A-1 varnish. In the blending examples and the examples, the components (mass parts) of the various examples shown in the comparative examples were blended in a ratio of the blending examples, and the mixture was prepared by mixing with a mixer, and then subjected to kneading by a three-roller honing machine to prepare photosensitivity for solder resist. Resin composition. Here, the degree of dispersion of the obtained photocurable resin composition was 15 μm or less in the measurement of the particle size by a grindmeter manufactured by Erichsen Co., Ltd. Further, the number of the components in the table indicates the parts by mass. Comparative Example 1 of Tables 1 and 2 refers to an example in which an oxime ester-based photopolymerization initiator is blended without red colorant or yellow colorant; Comparative Example 2 refers to blending a red colorant or a yellow colorant. An example in which an oxime ester photopolymerization initiator is not blended. Comparative Example 1 of Tables 3 and 4 refers to an example in which an oxime ester-based photopolymerization initiator is blended without a red colorant or a yellow colorant; Comparative Example 2 refers to an unblended -37-200910006 oxime ester system. An example of a photopolymerization initiator, a red colorant or a yellow colorant. Admixture A component A-1 varnish 154 parts (solid component 100 parts) B component amine hydrazine compound Schedule C component photopolymerization initiator Schedule D component dipentaerythritol hexaacrylate (manufactured by Nippon Kasei Co., Ltd.) 20 parts E component phenol novolak type epoxy resin (DEN-431, manufactured by Dow Chemical Co., Ltd.) 15 parts of dimethicone type epoxy resin (YX-4000, manufactured by Japan Epoxy Resins Co., Ltd.) 25 parts of other components barium sulfate (barium sulfate B3 0 manufactured by Seiko Chemical Co., Ltd.) 100 parts thermosetting catalyst dicyandiamide 0.3 parts heat curing catalyst melamine 5 parts pigment table polyoxyalkylene defoamer 3 parts DPM (dipropylene glycol monomethyl ether) 5 parts Table 1, 2 In addition to the above blending, there are examples and comparative examples in which the components of (B) (C) and the coloring agent are added. The characteristic evaluation at this time was evaluated using a 35 5 nm laser exposure machine manufactured by Orbotech. -38- 200910006

Comparative example fN P 〇τ-Η ί〇ο 00 〇in 〇m ο 卜〇<N Ο <Ν Ο ITi ο Ο (Ν Ο (Ν oo oo 00 〇(Ν Ο CN Ο oo o {|¥ inch 〇1〇*·η ο m 〇y-^ (N 〇»—Η 〇355nm laser exposure photopolymerization initiator (c-ir1 photopolymerization initiator (C-2^2 photopolymerization initiator) (C_3r3 photopolymerization initiator (C-4)+4 Λ ¢3 ^ _ S fine (1 •— ϋ m, ω _ g Cl S ϋ (Ν Ί§π; t# ϊ ¢1 a i_j &0酞 Turnip Blue CIPigment Blue 15:3 Machine 1 5 ¢3 1 CO -39- 200910006 [z® Comparative Example 400 〇ω <1 < ◎ Light Blue § 〇V-Η υ <] 〇〇 〇X 00 铢〇Α or C 〇〇〇〇〇 Μ § A or C 〇〇〇〇〇\〇§ A or C 〇〇〇〇〇A or C & & 〇〇〇〇 〇舾<〇〇〇〇<] CN < 〇〇〇〇 ◎ < 〇〇〇〇 ◎ 355 nm laser exposure case tone rO 〇 B forging image (μιη) line shape Solder heat resistance and corrosion resistance characteristics Electroless gold plating Acid resistant copper circuit color change eiIM^s13.2m3lD^.28dsBqG)z.06£pI : inch* (Ms crocodile ^-0)-1乂«-€-^^-116- («尘£13拼«&-^9-«\1-6]-1_\]: 3* belongs to -6-jian («&-SM«dust K])-<N: I* -40- 200910006 In Tables 3 and 4, the 355 nm laser exposure machine manufactured by Orbotech Co., Ltd. used in Tables 1 and 2 was used to evaluate the characteristics by using ORC company EXP-2960 equipped with a mercury short arc lamp.

Comparative example 〇 l〇o inch ο ^s〇o ο (N Example in Ο VO (N 〇(N o ^T) o Ο (N 〇&lt;N 〇00 om in ο Ό (N 〇&lt;N 〇oo o (Ν ο 〇o Ύ—* in ο r—1 Ο ο Ον ο Mercury short arc light polymerization initiator (c-ir1 photopolymerization initiator (C-2)+2 photopolymerization initiator ( C-3)d Photopolymerization initiator (C-4)+4 ^ Si _ S ¢) ω Fine (&amp; 〇: ut^· 1丨― 蘅$ _ g i0] s HH ϋ inch VO (NS ω _ I ¢1 a 酞 Turnip Blue CIPigment Blue 15:3 ¢1 | ^ 〇OO -41 - 200910006 [Inch patrol comparison example light blue 400 Α or C &lt; 〇〇〇X inch light blue 〇g υ &lt; 〇〇〇X m ,丨— § &lt;&lt;&lt;&lt; 〇Example to invite &lt; 〇〇〇〇〇g 8 &lt; 〇〇〇〇〇m § &lt; 〇〇〇〇〇CN Ms &lt; 〇〇〇〇〇 yellow ο &lt; 〇〇〇〇 &lt; Ο y 沄c 〇〇〇〇 ◎ as y ο &lt; 〇〇〇〇 ◎ Mercury short arc lamp tone sensitivity (m〗 / cm2) Image (μπι) line Shape solder heat resistance and erosion resistance electroless gold plating acid resistant copper circuit discoloration -42- 200910006 Performance evaluation: <Optimum exposure amount / sensitivity> Polishing roller (buff roll) honing copper thickness 35μηι circuit pattern substrate after 'washing, drying Thereafter, the photocurable resin composition of the above examples and comparative examples was completely applied by a screen printing method, and dried in a hot air circulating drying oven at 80 ° C for 60 minutes. A direct drawing device for a semiconductor laser having a wavelength of 355 nm or an exposure device equipped with a mercury short-arc lamp is exposed by a Step tablet (Kodak No. 2) to develop in 60 seconds (30 ° C, 〇. 2 MPa ' 1 mass) When the pattern of the Step tablet remaining in the % sodium carbonate aqueous solution is 7 segments, it is an optimum exposure amount. <Resolution and line shape> After polishing the honing line/300/300, copper-thickness 35μπι circuit pattern substrate, after washing and drying, the light of the examples and comparative examples was applied by screen printing. A curable resin composition at 80. (: The hot air circulating drying oven was dried for 30 minutes. After drying, exposure was performed using a direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm or an exposure device equipped with a mercury short arc lamp. It is used for direct drawing data or a mask for drawing lines of 20/ 30/40/50/60/70/80/90/100 μηι in the pitch portion. The exposure amount is the optimum exposure amount for the photocurable resin composition. The active energy ray was irradiated to the ground. After the exposure, development was carried out by using a 10% by mass aqueous solution of sodium carbonate, and the pattern was drawn, and the cured coating film was obtained by a heat hardening treatment at 150 ° C for 60 minutes. -43- 200910006 The minimum residual line of the cured coating film of the photocurable resin composition for solder resist resist obtained is obtained by using an optical microscope adjusted to 200 times (resolution). After the mirror processing, the upper diameter, the lower diameter, and the film thickness of the minimum residual line of the cured coating film were measured using an optical microscope adjusted to 1,000 times. The shape at this time was A to E as shown in the figure. Evaluation (line shape). The following is a pattern diagram at the time of development. In particular, the case where A is evaluated is that the offset of the design 値 is within 5 μηη of the upper and lower portions of the line. ΑEvaluation: ideal state of design twist B evaluation: development resistance The evaluation of the surface layer by insufficient etching, etc., C evaluation: undercut state D evaluation: E evaluation due to thick lines such as halo: the thick line and undercut of the surface layer are generated, not limited to A evaluation, C evaluation, D evaluation It can also be used as a grade for solder resists. For this reason, B evaluators have insufficient surface hardenability and poor appearance and electrical characteristics. E evaluators use lines and undercuts to be easily peeled off, and are not used as solder resists. Grade test: Evaluation of substrate preparation method: On the copper foil substrate on which the pattern was formed, the composition of each of the above examples and comparative examples was completely coated by screen printing, and dried at 8 ° C for 20 minutes. And let it cool to room temperature. The substrate is directly exposed to a semiconductor laser equipped with a maximum wavelength of 355 nm or an exposure device equipped with a mercury short arc lamp to expose the solder resist pattern at an optimum exposure. -44- 20091 0006 A 1% Na2C03 aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 〇 2 MPa for 60 seconds to obtain a photoresist pattern. The substrate was irradiated with ultraviolet light at a cumulative exposure of 1 OOO mJ/cm 2 in a UV transfer furnace. After that, it was heated at 150 ° C for 60 minutes and then hardened. The obtained printed substrate (evaluation substrate) was evaluated as follows. <Color of coating film> Solder resists of the above-mentioned Examples and Comparative Examples The color of the cured product was visually judged. <Solder heat resistance> The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath previously set at 26 (TC), and the flux was washed with denatured alcohol. Thereafter, the expansion and peeling of the photoresist layer visually observed were evaluated. The criteria are as follows. 〇: Even if it is repeated 3 times or more for 1 〇 second, there is no peeling. △: If it is repeated three times or more and immersed for one second, there is a slight peeling. X: The film is swelled and peeled off in the photoresist layer after being immersed for 3 sec. within 3 sec. <Electrical corrosion resistance> An evaluation substrate was produced under the above conditions using a comb-shaped electrode B sample (c 〇up ο η ) of IPC B-25 instead of the copper foil substrate, and a DC 1 0 0 V bias was applied to the comb-shaped electrode. The voltage was confirmed at a constant temperature and humidity chamber of -85 °C, 8 5 % R · Η · -45-200910006, and the migration after 〇〇〇 hours. The criterion is as follows. 〇: No change at all △: Only a few changers X: Migration generators <electroless gold plating resistance> Use a commercially available electroless nickel plating bath and an electroless shovel gold bath with nickel 〇· 5 μπι, gold The plating was performed under the conditions of 0 · 0 3 μηι, and the peeling of the photoresist layer or the presence or absence of plating penetration was evaluated by tape stripping, and then immersed in the solder bath for 10 seconds under the test conditions of the solder heat resistance. After washing and drying, tape stripping was performed to evaluate the presence or absence of peeling of the photoresist layer. The benchmark is as follows. Hey: There is no change at all. △: After the plating, some infiltration was observed and the peeling of the solder after heat resistance was observed. X: Peeled after plating. <Acid resistance> The evaluation substrate was immersed in an aqueous solution of 10 v〇i% h 2 so4 at room temperature for 30 minutes, and it was confirmed that the penetration or the coating film was eluted, and the peeling by tape removal was confirmed. The judgment criteria are as follows. 〇: No penetration, dissolution, or peeling. △: It was confirmed that there was little infiltration, dissolution or peeling. X : A large amount of infiltration, dissolution or peeling was confirmed. -46-200910006 <Discoloration of copper circuit> Further, the evaluation substrate was heated at 150 °C for 2 hours, and the degree of discoloration on the copper circuit was judged as follows. ◎: There is no discoloration at all. 〇: There is much discoloration compared to the initial stage, but there is no difference between the thin part and the thick part of the photoresist. △: The difference between the thin portion and the thick portion where there is no discoloration is observed. X: The thin portion of the photoresist is discolored, which is significantly different from the thick portion. As is apparent from the results shown in Tables 1 to 4, the examples of the present invention are excellent in sensitivity, resolution, line shape, and discoloration of a copper circuit. On the other hand, the comparative examples which are not blended with the coloring agent of the present invention are excellent in sensitivity, resolution, line shape, and copper circuit discoloration as in the embodiment of the present invention. In addition, in the additional test, a direct drawing device (Mercurex manufactured by Otsuka SCREEN (DAINIPPON SCREEN) Co., Ltd.) equipped with an ultrahigh pressure mercury lamp was used instead of the exposure apparatus equipped with the high pressure mercury lamp, and the composition of Examples 9 to 15 was evaluated. Substrate. When the results of the coating film characteristics were evaluated, the same results were obtained when an exposure machine equipped with a mercury short arc lamp was used. [Simple description of the drawing] -47- 200910006 [Fig. 1] is an explanatory diagram showing the Munsell hue circle. Fig. 2 is a schematic view showing the cross-sectional shape of the resin composition obtained by exposure and development, and A to E show the shapes of the evaluations which are different from each other. [Description of main component symbols] 1 a : Design of line width 値 1 b : Resin composition after exposure and development 1 c : Substrate -48-

Claims (1)

200910006 X. Patent application scope 1. A photocurable resin composition which can be developed by an aqueous alkali solution, which comprises (A) a resin containing a carboxylic acid, (B1) a red coloring agent, and (C) an oxime ester photopolymerization. A compound having two or more ethylenically unsaturated groups in the initiator and (D) molecule. 2. A photocurable resin composition which can be developed with an aqueous alkali solution, comprising (A) a carboxylic acid-containing resin, (B2) a yellow colorant, and (C) an oxime ester-based photopolymerization initiator; D) A compound having two or more ethylenically unsaturated groups in the molecule. 3. The photocurable resin composition which can be developed with an aqueous alkali solution according to the first aspect of the patent application, which contains one selected from the group consisting of yellow coloring agent (B2) and blue coloring agent (B3) or Two kinds. 4. The photocurable resin composition according to any one of claims 1 to 3, wherein the oxime ester photopolymerization initiator (C) is an oxime ester represented by the following general formula (I) A photopolymerization initiator, which further contains an α-aminoacetophenone photopolymerization initiator represented by the following general formula (Π) and a mercaptophosphine oxide represented by the following general formula (ΠΙ) One or two kinds of photopolymerization initiators, [Chem. 1] C = N - ο - c - R 2 ... (| ) I, II R1 〇 (wherein R 1 is a hydrogen atom, a phenyl group (which may be An alkyl group having a carbon number of 1 to 6 and a phenyl ' or a halogen atom; and having a carbon number of 1 to 2 Å (which may be substituted by 1 to 49 to 200910006 or more hydroxyl groups, and may have an alkyl group in the middle thereof) More than one oxygen atom) 'A carbon ring of 5 to 8 ring, Alkanoyl or phenyl fluorenyl group of 2 to 20 carbon atoms (which may be alkyl or phenyl group having a carbon number of 1 to 6) Substituting), R2 is a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and an alkane) There may be more than one in the middle of the chain An oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoinyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group)) (wherein R3 and R4 are each independently an alkyl group or an aralkyl group having 1 to 12 carbon atoms; and R5 and R6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 bonds; Formation of a cyclic alkyl ether group) [Chemical 3] P-C—(III) -50- 200910006 (wherein R7 and R8 are each independently a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexyl group, a cyclopentyl group, an aryl group, An alkoxy group, or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group, wherein R7 and R8 = one is R-C(=0)- group (wherein R can be a carbon number of 1~ 20 pain base)). 5. The photocurable resin composition of the fourth aspect of the invention, wherein the oxime ester photopolymerization initiator (C) represented by the above general formula (I) is represented by the following formula (IV) Ester photopolymerization initiator, 光 / / / / c c ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra ra The starting agent (C) is an oxime ester photopolymerization initiator represented by the following general formula (V), [Chem. 5] -51 - 200910006 (In the formula, R9 is a hydrogen atom, a halogen atom, a carbon number of 1 to 12, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoinyl group, and a carbon number of 2 to 12) Alkoxy group having a carbon number of 2 to 12 (when the carbon number of the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the middle of the chain may have one or more. Oxygen atom), or phenoxycarbonyl, RIO, R12 are each independently phenyl (can be substituted by a group of 1 to 6 carbon atoms, phenyl or halogen atom), alkyl having 1 to 20 carbon atoms (can be One or more hydroxyl groups may be substituted, one or more oxygen atoms may be present in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoinyl group (which may be carbonized) Substituted by an alkyl group of 1 to 6 or a phenyl group), R11 is a hydrogen atom, a phenyl group (which may be substituted by a substituent having a carbon number of 1 to 6, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms. (may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoinyl group (which Alkane which can be carbon number 1~6 Or phenyl substituted)). The photocurable resin composition according to any one of claims 1 to 3, wherein the crucible contains (E) a thermosetting component. 8. The photocurable resin composition of claim 3, wherein the 'composition' is a solder resist having a color tone selected from the group consisting of blue, green, orange, and purple. A photocurable dry film obtained by applying a photocurable resin composition according to any one of claims 1 to 3 to a carrier film and drying it. (1) A hardened material obtained by photohardening a photocurable resin composition according to any one of claims 1 to 3 to 52 to 200910006. A cured product obtained by photohardening a dry film of claim 9 of the patent application. A hardened material obtained by photohardening a copper photocurable resin composition according to any one of claims 3 to 3. A cured product characterized by the dry film of claim 9 of the patent application, which is photohardened on copper. A printed wiring board having an insulating layer, which is characterized in that the photocurable resin composition according to any one of claims 1 to 3 is photohardened and then thermally cured. A printed wiring board having an insulating layer, which is characterized in that the dry film of claim 9 of the patent application is subjected to photohardening and then thermally hardened. A printed wiring board having an insulating layer characterized by containing a red coloring agent (B 1 ). The printed wiring board of claim 16 wherein the red colorant (B 1 ) is a red coloring agent which does not contain any of a halogen and an azo group. -53-