TWI401531B - A photohardenable resin composition and a hardened product thereof - Google Patents

Description

Photocurable resin composition and cured product thereof

The present invention relates to a colored photocurable resin composition of a halogen-free indocyanine green. More specifically, the present invention relates to a colored photocurable resin composition containing no halogen-containing phthalocyanine green, and particularly provides a solder resist layer excellent in masking property due to oxidation of a copper circuit.

Typically, the solder resist is formed to protect the copper loop. On the other hand, it also has the effect of discoloration, electrochromism, smashing of the copper circuit, and dirt caused by the heat or moisture of the copper circuit.

The solder resist is applied to a glass epoxy substrate formed by a copper circuit, and an image is formed by exposure, and the film pattern is formed by development and thermal 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 and thin on the copper circuit, at the edge of the copper circuit. The part is even thinner.

In the case where the thickness of such solder resist is different, it is difficult to mask the copper circuit from the appearance. Therefore, for the solder resist, a coloring agent is usually blended, and the discoloration of the copper circuit or the like is hard to see by making the concentration thick.

Recently, the solder resist is a green phthalocyanine green which is a green coloring agent in view of reducing the environmental load, and a phthalocyanine blue having no halogen atom and a yellow coloring agent having no halogen atom are generally used. Green solder resist (for example, refer to Patent Document 1).

Also, it is clearly known as halogen-free from the appearance (halogen free In addition, phthalocyanine blue is also used alone as a blue solder resist.

However, compared to the green color made of phthalocyanine green, the blue solder resist or the green solder resist formed by the blue colorant and the yellow colorant is weakly masked and cannot be sufficiently The case where the function as a coloring agent which is difficult to see when the appearance is poor is realized, and the following description will be apparent.

That is, the current solder resist is formed by photohardening, and finally subjected to a heat hardening treatment. The treatment temperature at this time is generally about 150 to 60 minutes at 150 ° C, but the temperature or time is not necessarily determined by the substrate manufacturer. As a result, in particular, in the case where the processing time with a high processing temperature is long, the blue solder resist photoresist having poor masking property cannot cover the problem of discoloration on the substrate due to oxidation of the copper circuit. This problem is also the same in the green solder resist resist using a halogen-free blue colorant and a yellow colorant, and it has been confirmed by the inventors that the masking property is weaker than that of the phthalocyanine green.

Further, when a marking ink is applied to the substrate, after the solder resist is cured, the mark is printed and thermally cured, so that the discoloration of the copper circuit is accelerated, and the appearance problem is further serious.

Further, in order to correct the warpage of the substrate when the solder resist is thermally hardened, pressure and heat are applied to the entire substrate, and the discoloration of the copper circuit is accelerated in the same manner.

Among the discoloration of such a copper circuit, the worst phenomenon is that it is on the same copper circuit, but only the edge of the circuit (the portion where the photoresist is thinned) is in a state of discoloration. In this case, when the substrate is inspected or actually assembled, it is inconsistent with the inspection data, and even if it is a good product, it becomes defective. Conversely, if the color is confirmed on the copper circuit and the other parts are uniformly identified, it will not occur. It's a bad situation.

The case of such discomfort is remarkable in the case where a coloring agent such as phthalocyanine blue having no halogen atom is used in place of phthalocyanine green (halogen-free coloring agent).

[Patent Document 11] Japanese Laid-Open Patent Publication No. 2000-7974 (Patent Application Scope, Prior Art)

Therefore, the present invention provides a colored photocurable resin composition which is capable of forming a solder resist layer having excellent masking properties such as discoloration due to oxidation of a copper circuit.

As a result of intensive studies by the inventors of the present invention, it has been found that by using a colored photocurable resin composition which is at least a red coloring agent as a coloring agent, it is possible to solve the masking of the conventional solder resist resist using a halogen-free coloring agent. Further, in view of the above problems, by using a halogen-free red coloring agent, it is possible to achieve the present invention without deteriorating the masking property and reducing the halogen content of the solder resist layer.

That is, the present invention is a photocurable resin composition which can be developed with an aqueous alkali solution, and is characterized by containing (A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, and (C) having two or more molecules. a compound of an ethylenically unsaturated group, and (D) a red colorant.

The photocurable resin composition of the present invention is in one aspect, and may contain (E1) a blue colorant (for example, phthalocyanine blue) and/or (E2) yellow colorant in addition to the red colorant (D). The color tone can be blue, green, purple or orange.

Further, the photocurable resin composition of the present invention is in one aspect, and the red coloring agent (D) is a red coloring agent which does not contain any of a halogen and an azo group.

Further, the photocurable resin composition of the present invention is in one aspect and further contains (F) a thermosetting component.

Further, the photocurable resin composition of the present invention is used in one aspect for coating on copper.

Furthermore, the present invention is a photocurable dry film obtained by applying the photocurable resin composition to a carrier film and drying it.

Further, in another aspect of the invention, the photocurable resin composition is a cured product of blue, green, purple or orange.

Further, in another aspect of the invention, the dry film is a cured product of blue, green, purple or orange.

Further, the present invention is a printed wiring board having a solder resist layer formed of the cured product on a substrate on which a copper circuit is formed in another aspect.

According to the present invention, it is possible to provide a blue, green, purple or orange colored solder resist layer which is excellent in masking property due to oxidation of a copper circuit.

. In particular, it is effective as a blue solder resist resist which is replaced with a general-purpose blue solder resist resist having a problem of masking. Further, the solder resist layer obtained by the present invention has an extremely low halogen content and a significant decrease in the amount of halogen gas generated when the coating film is burned.

Hereinafter, the present invention will be described in detail.

As described above, the photocurable resin composition of the present invention is characterized in that at least a red coloring agent (D) is used as a coloring agent in place of the conventional halogen-containing phthalocyanine green, and in one aspect, in addition to red In addition to the colorant (D), a blue colorant (E1) and/or a yellow colorant (E2) are further contained, and the color tone thereof is a photocurable resin composition of blue, green, purple or orange.

Therefore, the coloring agent of the present invention will first be described. In the present invention, the coloring agent can be any conventional one, and can be any of a pigment, a dye, and a coloring matter. However, in terms of reducing environmental load and affecting the human body, it is preferred that halogen is not contained.

As a red coloring agent (D), monoazo type, bisazo type, azo lake type, benzimidazolone type, anthracene type, diketopyrrolopyrrole type, condensed azo type, hydrazine Specifically, the oxime system, the quinacridone system, and the like may be exemplified by a color index (CI; The Society of Dyers and Colourists, Inc.) number as follows.

-monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15, 16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269; -Bisazo Department: Pigment Red 37, 38, 41; Monoazo lake: 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 series: Pigment Red 171,175,176,185,208;-lanthanide:Solvent Red 135,179;Pigment Red 123 , 149,166,178,179,190,194,224;-diketopyrrolopyrrole: Pigment Red 254,255,264, 270,272;-condensed azo system: Pigment Red 220,144,166,214,220,221,242;-lanthanide: Pigment Red 168; 177,216; Solvent Red 149,150,52,207; Pyridone system: Pigment Red 122, 202, 206, 207, 209.

Although it is not particularly limited, it is preferable to use a red coloring agent which does not contain an azo group from the viewpoint of safety and harmlessness.

The blue coloring agent (E1) 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 added. And Colourists company issued) number.

- Pigment system: Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60; - Dye system: Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70.

A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

Examples of the yellow coloring agent (E2) include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindane type, an anthraquinone type, and the like, and specifically may be added as follows. The color index number.

- lanthanide: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202; - isoindane system: Pigment Yellow 110, 109, 139, 179, 185; - condensed azo system: Pigment Yellow 93, 94, 95, 128, 155, 166, 180; - benzimidazolone series: Pigment Yellow 120, 151, 154, 156, 175, 181; - monoazo system: Pigment Yellow 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 system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Although it is not particularly limited, it is preferable to use a yellow coloring agent which does not contain an azo group from the viewpoint of safety and harmlessness.

In the present invention, the blending ratio of the red colorant and the blue colorant and/or the yellow colorant is such that the obtained photocurable resin composition or the solder resist layer formed of the cured film is a desired color tone. Specifically, it can be made blue, green, purple or orange in a sufficient ratio.

In the present invention, the photocurable resin composition of the present invention or its hardening The film exhibits blue, green, purple, and orange colors, which are those which are perceived by the naked eye as being blue, green, purple, and orange. Specifically, the appearance of the photocurable resin composition and the hardened film thereof is measured by the method specified in JIS Z8721. When the display is performed, the Munsell hue ring is supervised by the Japan Color Research Institute. Series 2 Munsell System Japan Color Research Co., Ltd. issued; refer to Figure 1), from 5BG to less than 3P (blue), from 9Y to less than 5BG (green), from 3P to less than 7RP ( Purple), a hue range from 9R to less than 7YR (orange), and preferably has a chroma of 1 or more and less than 16; a brightness of 1 or more is less than 9, and a better system chroma is 2 or more and less than 15; The brightness is 2 or more and less than 9.

The specific blending ratio is also affected by the type of the coloring agent used or other additives, and cannot be discussed in general, but generally, the coloring ratio is red coloring agent (D): blue coloring agent (E1): yellow Colorant (E2) = 1:0~50:0~50. Further, in order to perform sufficient coloring, the ratio of the total amount of the composition of the red coloring agent (D), the blue coloring agent (E1), and the yellow coloring agent (E2) is 0.05 to 3.0% by mass. good.

In the present invention, in addition to the above coloring agent, a coloring agent such as purple, orange, brown, black or the like may be added for the purpose of adjusting the color tone, and specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI 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, CI Pigment Orange 49, CI Pigment Orange 51, CI 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.

Next, the resin (A) containing a carboxylic acid will be described.

As the carboxylic acid-containing resin (A) contained in the photocurable resin composition of the present invention, a well-known resin compound containing a carboxylic acid in a molecule can be used. Further, the carboxylic acid-containing photosensitive resin (A') having an ethylenically unsaturated double bond in the molecule is preferred in terms of photocurability or development resistance.

Specifically, the following enumerated resins are mentioned.

(1) to (9) and the like: (1) a carboxylic acid-containing copolymer resin which has an unsaturated carboxylic acid such as (meth)acrylic acid and one or more of them. (2) A photosensitive resin containing a carboxylic acid, which is an unsaturated carboxylic acid such as (meth)acrylic acid, and one or more kinds of other unsaturated double bonds, which are obtained by copolymerization of a compound having an unsaturated double bond. a copolymer of a compound of a bond, which is a compound having an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate and an unsaturated double bond, Or (meth)acrylic acid chloride or the like 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 The copolymer is obtained by reacting an unsaturated carboxylic acid such as (meth)acrylic acid, and reacting the formed secondary hydroxyl group with a polybasic acid anhydride, and (4) a photosensitive resin containing a carboxylic acid, which has An acid anhydride of an unsaturated double bond such as maleic anhydride or a copolymer having a compound having another unsaturated double bond, having a hydroxyl group and an unsaturated double bond such as 2-hydroxyethyl (meth) acrylate (5) A photosensitive resin containing a carboxylic acid, which is obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride (6) A photosensitive resin containing a hydroxyl group and a carboxylic acid, which is a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, which is reacted with a saturated or unsaturated polybasic acid anhydride to form a carboxylic acid as a molecule. a compound having an epoxy group and an unsaturated double bond Further, (7) a photosensitive resin containing a carboxylic acid, which is an alcoholic hydroxyl group which reacts a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and at least one alcoholic hydroxyl group in one molecule with an epoxy group. The reaction product of a compound other than the reactive group is determined by a reaction of a saturated or unsaturated polybasic acid anhydride, and (8) a photosensitive resin containing a carboxylic acid having at least two oxygen heterocycles in one molecule. A polyfunctional oxetane compound of a butane ring, 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 carboxylic acid-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid to obtain a carboxylic acid-containing resin obtained by reacting a polybasic acid anhydride, and further having an epoxy resin 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 preferred, 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)acrylates, which are collectively referred to as acrylates, methacrylates, and the like, have the same performances.

The carboxylic acid-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, and can be developed in an aqueous alkali solution.

Further, the acid value of the carboxylic acid-containing resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid value of the carboxylic acid-containing resin is less than 40 mgKOH/g, alkali development is difficult. On the other hand, when it exceeds 200 mg KOU/g, it is necessary to make the line thinner by the dissolution of the exposed portion of the developer. In the case where the exposed portion and the unexposed portion are not distinguished from each other, the dissolution and peeling in the developer are facilitated, and the drawing of the normal photoresist pattern becomes difficult, which is not preferable.

Further, the weight average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and further preferably in the range of 5,000 to 100,000. Weight average molecular weight is not up to At 2,000 hours, the non-stick property was poor, and the moisture resistance of the coating film after the exposure was poor, and the film was reduced at the time of development, and the resolution was poor. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is poor.

The blending amount of the carboxylic acid-containing resin (A) is in the total composition, and is preferably 20 to 60% by mass, more preferably 30 to 50% by mass. When the amount is less than the above range, the film strength is lowered, which is not preferable. On the other hand, in the case of more than the above range, the viscosity is high and the coatability and the like are lowered, which is not preferable.

Next, the photopolymerization initiator (B) will be described.

The photopolymerization initiator (B) may, for example, be acetophenone, 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxy-2-phenylbenzene. Ketone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butyl Acetophenones such as ketone-1, N,N-dimethylaminoacetophenone; diphenyl ketone, methyl diphenyl ketone, 2-chlorodiphenyl ketone, 4,4'-dichloro bis Phenyl ketone, 4,4'-bisdimethylaminodiphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, Michler's ketone, 4-benzylidene- Diphenyl ketones such as 4'-methyldiphenyl sulfide; benzyl; benzamidine, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutylene a benzoin ether such as ether; a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthiophene Thioxanthone such as ketone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; 2-methylindole, 2- Anthraquinones such as ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, 2-amino hydrazine, 2,3-diphenyl hydrazine; Organic peroxides such as cumene peroxide; 2,4,5-triaryl imidazole dimer, riboflavin tetra butyrate, 2-mercaptobenzimidazole, 2-mercaptobenzene a thiol-based compound such as oxazole or 2-mercaptobenzothiazole; 2,4,6-parallel-s-three , an organic halogen compound such as 2,2,2-tribromoethanol or tribromomethylphenylhydrazine; 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis(2,4,6- Trimethylphenyl fluorenyl)-phenylphosphine oxide) and the like. These compounds may be used singly or in combination of two or more.

Further, the photopolymerization initiator (B) may be used in combination of one or more kinds of, for example, ethyl N,N-dimethylaminobenzoate and isoamyl N,N-dimethylaminobenzoate. a tertiary amine such as pentyl-4-dimethylaminobenzoate, triethylamine or triethanolamine, bis(η5-cyclopentadienyl)-bis(2,6-difluoro-3- Titanocenes such as (1H-pyrrol-1-yl)phenyl)titanium; 2-(diethyl ether decylmethyl) thioxanthene-9-one, 1,2-octanedione, 1-[ 4-(phenylthio)-,2-(O-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole- A photo sensitizer of an oxime ester such as 3-yl]-, 1-(O-ethenyl fluorene) is used.

A preferred combination of the above photopolymerization initiator (B) is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (for example, manufactured by Ciba Specialty Chemicals Co., Ltd. , IRGACURE 369: IRGACURE is a registered trademark) and bis(η5-cyclopentadienyl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium (eg Ciba Specialty Chemicals) Company-made, IRGACURE 784) combination; 2,4,6-trimethylphenylnonyldiphenylphosphine oxide a compound (for example, Lucirin TPO manufactured by BASF) in combination with 2-(ethylhydrazinylmethyl)thioxanthene-9-one (for example, CGI-325, manufactured by Ciba Specialty Chemicals Co., Ltd.); or 2,4,6-trimethyl Benzobenzyldiphenylphosphine oxide (for example, Lucirin TPO manufactured by BASF) and bis(2,4,6-trimethylphenylhydrazino)-phenylphosphine oxide (for example, IGAGCURE 819, manufactured by Ciba Specialty Chemicals Co., Ltd.) The combination of etc.

In addition, the preferred range of the amount of the photopolymerization initiator (B) to be used is preferably 1 to 30 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the carboxylic acid-containing resin (A). ~25 parts by mass ratio. When the blending ratio of the photopolymerization initiator is less than the above range, the photocurability of the resulting composition is deteriorated. On the other hand, when the amount is more than the above range, the properties of the obtained cured coating film are deteriorated, and the storage stability of the composition is deteriorated, which is not preferable.

Next, a compound having two or more ethylenically unsaturated groups in the molecule will be described.

The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation of an active energy ray to form the carboxylic acid-containing resin (A). ) is insoluble in the aqueous alkali solution or helps insoluble. 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 isocyanurate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; C Polyacrylates such as olefinic acid esters, bisphenol A diacrylates, and such phenolic ethylene oxide adducts or propylene oxide adducts; glycerol condensate a polyacrylate of a glycidyl ether such as glyceryl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl isocyanurate; and melamine acrylate, and/or corresponding to the above Each methacrylate of acrylate or the like.

Further, an epoxy acrylate resin which can react a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, or a hydroxyl group such as pentaerythritol triacrylate whose hydroxyl group of the epoxy acrylate resin is further exemplified An epoxy urethane acrylate compound obtained by reacting an ester 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 ratio of the compound (C) 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 blending amount is less than 5 parts by mass, the photocurability is lowered, and the alkali developing system which is irradiated with the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered and the coating film becomes brittle, which is not preferable.

Next, the thermosetting component (F) will be described.

In order to impart heat resistance to the photocurable resin composition of the present invention, a thermosetting component (F) may be added. Especially good, there are 2 in the molecule. A thermosetting component (F) of a cyclic ether group and/or a cyclic thioether group (hereinafter, simply referred to as a cyclic (thio)ether group).

The thermosetting component (F) having two or more cyclic (thio)ether groups in such a molecule is a cyclic ether group having a ring of 3, 4 or 5 members in the molecule, or a cyclic thioether group. Any one of the compounds having two or more types of the group, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (F-1); a compound having at least two or more oxetanyl groups, that is, a polyfunctional oxetane compound (F-2); a compound having at least two or more thioether groups in the molecule, that is, a surface sulfide An epoxy resin (F-3) or the like.

Examples of the polyfunctional epoxy compound (F-1) include EPIKOTE 828, EPIKOTE 834, EPIKOTE 1001, and EPIKOTE 1004 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON 840, EPICLON 850, and EPICLON 1050 manufactured by Dainippon Ink and Chemicals. EPICLON 2055, EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd.; Araldite 6071, Araldite from Ciba Specialty Chemicals 6084, Araldite GY250, Araldite GY260, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries, Ltd.; AER330, AER331, AER661, AER664, etc. manufactured by Asahi Kasei Industrial Co., Ltd. Bisphenol A type epoxy resin (both trade names); EPIKOTE YL903 manufactured by Japan Epoxy Resins Co., Ltd., Dainippon Ink Chemistry EPICLON 152, EPICLON 165 manufactured by Industrial Co., Ltd., EPOTOHTO YDB-400, YDB-500 manufactured by Dongdu Chemical Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Araldite 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy manufactured by Sumitomo Chemical Industries Co., Ltd. ESB-400, ESB-700, brominated epoxy resin of AER711, AER714, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.; EPIKOTE 152, FPIKOTF 154, manufactured by Japan Epoxy Resins Co., Ltd., DEN431 manufactured by Dow Chernical Co., Ltd. DEN438, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPOTOHTO YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., Araldite ECN1235 manufactured by Ciba Specialty Chemicals Co., Ltd. Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-Epoxy ESCN-195X, ESCN- by Sumitomo Chemical Industries, Ltd. 220, a novolac type epoxy resin of AER ECN-235, ECN-299, etc. (all trade names) manufactured by Rising Sun Chemical Co., Ltd.; EPICLON 830, J manufactured by Dainippon Ink Chemical Industry Co., Ltd. EPIKOTE 807 manufactured by Apan Epoxy Resins Co., Ltd., EPOTOHTO YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldite XPY306 manufactured by Ciba Specialty Chemicals Co., Ltd. (all trade names), bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin such as EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; EPIKOTE 604 manufactured by Japan Epoxy Resins Co., Ltd., manufactured by Dongdu Chemical Co., Ltd. EPOTOHTO YH-434, Araldite MY720 manufactured by Ciba Specialty Chemicals, glycidylamine epoxy resin of Sumi-Epoxy ELM-120 (both trade name) manufactured by Sumitomo Chemical Industries, Ltd.; Araldite CY manufactured by Ciba Specialty Chemicals Hydantoin type epoxy resin such as -350 (trade name); CELLOXIDE 2021 manufactured by DAICEL Chemical Industry Co., Ltd., Araldite CY175, CY179, etc. (all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd. YL-933 manufactured by Japan Epoxy Resins Co., Ltd., TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Co., Ltd., trihydroxyphenylmethane epoxy resin; YL-made by Japan Epoxy Resins Co., Ltd. 6056, YX-4000, YL-6121 (all trade names) and other bi-xylenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-made by Asahi Kasei Kogyo Co., Ltd. 30. Bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink and Chemicals Co., Ltd.; bisphenol A novolak epoxy resin such as EPIKOTE 157S (trade name) manufactured by Japan Epoxy Resins Co., Ltd. ; E by Epoxy Resins, Japan PIKOTE YL-931, tetraphenol ethane type epoxy resin of Araldite 163 (all trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.; Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. a heterocyclic epoxy resin; a diglycidyl phthalate resin such as BLEMMER DGT manufactured by Nippon Oil & Fats Co., Ltd.; a glycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tosho Kasei Co., Ltd.; Nippon Steel Chemical Co., Ltd. ESN- 190, ESN-360, Naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; HP-7200, HP-7200H, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd. An epoxy resin having a dicyclopentadiene skeleton; a glycidyl methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc. manufactured by Nippon Oil & Fats Co., Ltd.; and further cyclohexylmethylenediimide and a copolymerized epoxy resin of glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), and a CTBN modified epoxy resin (for example, manufactured by Dongdu Chemical Co., Ltd.) YR-102, YR-450, 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 preferable.

The above polyfunctional oxetane compound (F-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-) Oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-) 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylic acid Ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, or oligomerization thereof Polyfunctional oxetane such as a substance or a copolymer, and other oxetane and novolak resins, poly(p-hydroxystyrene), cardo type bisphenol a class, calixarene, calix resorcinol (calixresorcinarene), or with sesquiterpene oxide ( An etherified product of a resin such as a silsesquioxane). Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

The compound (F-3) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A-type surface sulfide resin YL7000 manufactured by Japan Epoxy Resins Co., Ltd., or the like. Further, by using the same synthesis method, a surface sulfide resin in which an oxygen atom of an epoxy group of a novolac type epoxy resin is substituted with a sulfur atom may be used.

The blending ratio of the thermosetting component (F) having two or more cyclic (thio)ether groups in the molecule is 1 equivalent to the carboxyl group of the carboxylic acid-containing resin (A), preferably 0.6~. A range of 2.5 equivalents, more preferably 0.8 to 2.0 equivalents. When the amount of the thermosetting component (F) 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, and heat resistance and alkali resistance are Electrical insulation and the like are lowered, which is not preferable. On the other hand, when it exceeds 2.5 equivalents, since the low molecular weight cyclic (thio)ether group remains on the dried coating film, the strength of the coating film and the like are lowered, which is not preferable.

In the photocurable resin of the present invention, when a thermosetting component (F) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst (G). Examples of the thermosetting catalyst (G) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole. Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyl Dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as a benzylamine; an anthracene compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine; and a commercially available product such as 2MZ manufactured by Shikoku Chemical Industry Co., Ltd. A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of imidazole-based compound), U-CAT3503N, U-CAT3502T (trade name of block isocyanate compound of dimethylamine) manufactured by SAN-APRO Co., Ltd., DBU , DBN, U-CATSA102, U-CAT5002 (all bicyclic guanidine compounds and their salts) and the like. In particular, it is not limited thereto, and a thermosetting catalyst of an epoxy resin or an oxetane compound may be used, or a reaction for promoting an epoxy group and/or an oxetanyl group and a carboxyl group may be used. It is also possible to use two or more kinds alone or in combination. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-III can also be used. 2-vinyl-4,6-diamino-S-three 2-vinyl-4,6-diamino-S-three ‧Iso-cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three . S-three of iso-cyanate adducts, etc. The derivative is preferably used in combination with the above-mentioned thermosetting catalyst as a function of the adhesion imparting agent.

It is sufficient that the blending amount of the thermosetting catalyst is a ratio of a general amount, for example, a resin containing a carboxylic acid (A) or a thermosetting component having two or more cyclic (thio)ether groups in the molecule. (F) 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

The photocurable resin composition of the present invention is formed by increasing the physical strength and the like of the coating film, and may be blended with a filler as needed. Such a filler can be used in the week For the purpose of customary inorganic or organic fillers, barium sulphate, spheroidal cerium oxide and talc are particularly preferred. Further, a compound having one or more ethylenically unsaturated groups or a NANOCRYL (trade name) XP 0396, XP manufactured by Hanse-Chemie Co., Ltd. in which the nano bismuth oxide is dispersed in the above polyfunctional epoxy resin (E1) may be used. 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP1045 (all product grade name) or Hanno-Chemie company's NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all products) Grade name). These may be used alone or in combination of two or more.

The blending amount of the filler is preferably 300 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 carboxylic acid-containing resin (A). When the blending amount of the filler exceeds 300 parts by mass, the viscosity of the photosensitive composition becomes high, the printability is lowered, and the cured product becomes brittle.

Further, the photocurable resin composition of the present invention is an organic solvent in which the synthesis or composition of the carboxylic acid-containing resin (A) is adjusted or the viscosity of the substrate or the carrier film is adjusted.

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 a glycol ether such as an alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether or triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate And esters such as dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; An aliphatic hydrocarbon such as an alkane or a decane; 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.

The photocurable resin composition of the present invention may further blend well-known heats such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, etc., as needed. Polymerization inhibitor; fine powder of cerium oxide, organic bentonite, montmorillonite, etc., known as tackifiers, polyoxyalkylene systems, fluorine-based, polymer-based defoamers and/or leveling agents, imidazole A well-known additive such as a decane coupling agent such as a thiazole system or a triazole system, an antioxidant, or a rust preventive agent.

Next, a dry film obtained by using the photocurable resin composition of the present invention, a cured product, and a printed wiring board having a solder resist layer formed of the cured product will be described.

The photocurable resin composition of the present invention 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, in particular, by laser light having a wavelength of 350 to 410 nm. The printed wiring board according to the present invention is obtained by photohardening in this manner and then thermally hardened.

Specifically, the following methods can be carried out to form a dry film and a cured product. , printed wiring board. 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, or the like, the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a tack-free coating. membrane. Further, the 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 a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous alkali carbonate solution) to form a photoresist pattern. Further, in the case where the composition of the thermosetting component (F) is contained, for example, heating is carried out at a temperature of about 140 to 180 ° C to thermally cure the carboxyl group of the carboxylic acid-containing resin (A) and two molecules in the molecule. The thermosetting component (F) of the above cyclic (thio)ether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.

In addition, even if the thermosetting component (F) 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).

Examples of the substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene, and PPO. ‧Cyanate ester Copper-clad laminates of all grades (FR-4, etc.) of other materials such as copper-clad laminates, such as high-frequency circuits, other polyimide films, PET films, glass substrates, ceramic substrates, and crystals. Round plate, etc.

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 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.

An exposure machine used for illuminating the active energy ray can be an exposure machine equipped with a laser direct drawing device (Laser direct imaging device), a metal halide lamp, or an (ultra) high pressure mercury lamp. A direct drawing device for an ultraviolet lamp such as an exposure machine equipped with a mercury short-arc lamp or an (ultra) high-pressure mercury lamp. If the active energy line uses laser light having a maximum wavelength in the range of 350 to 410 nm, it may be either a gas laser or a solid laser. Further, the exposure amount varies depending on the film thickness or the like, and is generally 5 to 200 mJ/cm ² , preferably 5 to 100 mJ/cm ² , and 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.

[Examples]

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 "parts" which appear below are all "mass parts" unless otherwise specified.

<Synthesis of a carboxylic acid-containing resin>

The carboxylic acid-containing resin (A) of the present invention was produced in accordance with the following synthesis.

220 parts of cresol novolac type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., "EPICLON" (registered trademark) N-695, epoxy equivalent: 220) was poured into four ports with a mixer and a reflux cooler. In the flask, 214 parts of carbitol acetate was added and dissolved by heating. Next, 0.46 parts of hydroquinone of a polymerization inhibitor and 1.38 parts of triphenylphosphine of a reaction catalyst were added. The mixture was heated at 95 ° C to 105 ° C, and 72 parts of acrylic acid was slowly dropped, and allowed to react for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 106 parts of tetrahydrophthalic anhydride was added thereto to cause a reaction for 8 hours. After cooling, the reaction solution (referred to as varnish (A-1)) was taken out. The carboxylic acid-containing resin-based solid obtained in this manner had an acid value of 100 mgKOH/g and a nonvolatile content of 65%.

<Examples 1 to 7 and Comparative Examples 1 to 2>

The varnish (A-1) obtained by the synthesis of the carboxylic acid-containing resin and the components shown in Table 1 were kneaded by three rolls at the blending ratios shown in the same table to obtain a photocurable resin composition.

The photocurable resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were evaluated for performance and characteristics in accordance with the following evaluation criteria. The results are shown in Table 2.

Performance evaluation: <optimal exposure / sensitivity>

A buff roll was used to polish a 35 μm copper circuit pattern substrate, and after water washing and drying, the photocurable resins of Examples 1 to 7 and Comparative Examples 1 and 2 were completely coated by screen printing. The composition was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, the step of exposure was carried out by using an exposure apparatus equipped with a metal halide lamp, and exposed by Step Terrace (Kodak No. 2) to develop in 60 seconds (30 ° C, 0.2 MPa, 1 mass % sodium carbonate aqueous solution). When the pattern of the tablet is 7 segments, it is used as the optimum exposure amount.

<Resolvability>

After the polishing roll polishing line/the circuit pattern substrate having a distance of 300/300 and a copper thickness of 35 μm, after being washed with water and dried, the photocuring properties of Examples 1 to 7 and Comparative Examples 1 and 2 were applied by screen printing. The resin composition was dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out using an exposure apparatus equipped with a metal halide lamp. The exposure pattern is used for direct drawing data or a mask for drawing lines of 20/30/40/50/60/70/80/90/100 μm in the pitch portion. The exposure amount is such that the active energy ray is irradiated to an optimum exposure amount of the photocurable resin composition. After the exposure, development was carried out by using a 1% by mass aqueous solution of sodium carbonate at 30 ° C, and the pattern was drawn, and 150 ° C × 60 minutes was passed. The hardening treatment is performed to obtain a hardened coating film.

The minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resist was obtained using an optical microscope adjusted to 200 times.

Characteristic test:

(Production of Evaluation Substrate) On the copper foil substrate on which the pattern was formed, the compositions of the above Examples 1 to 4 and Comparative Examples 1 and 2 were completely applied by screen printing, and dried at 80 ° C for 20 minutes, and Allow to cool to room temperature. For this substrate, an exposure apparatus equipped with a metal halide lamp was used, and the solder resist pattern was exposed at an optimum exposure amount, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 2 kg/cm ² for 60 seconds. , get the photoresist pattern. This substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ² in a UV transfer furnace, and then heated at 150 ° C for 60 minutes to be hardened. The obtained printed substrate (evaluation substrate) was evaluated for the following characteristics.

<Color of coating film>

With respect to the solder resists of the above examples and comparative examples, the color of the cured product was visually judged.

<Copper circuit discoloration>

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.

○: How much discoloration is compared with the initial period, but there is no thin photoresist at all. The difference between a part and a thick part.

△: The difference between the thin portion and the thick portion where there is no discoloration is observed.

×: The thin portion of the photoresist was observed to have discoloration, which was significantly different from the thick portion.

<Solder heat resistance>

The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with denatured alcohol, and then the expansion and peeling of the photoresist layer was visually observed. Evaluation. The judgment criteria are as follows.

○: No peeling was observed even if the immersion was repeated three times or more for 10 seconds.

△: If the immersion was repeated three times or more for 10 seconds, there was a slight peeling.

X: The film was swelled and peeled off in the photoresist layer after being immersed for 10 seconds within 3 times.

<electroless gold plating resistance>

Using an electroless nickel plating bath and an electroless gold plating bath of a commercially available product, plating was carried out under conditions of 0.5 μm of nickel and 0.03 μm of gold, and tape stripping was performed to evaluate the presence or absence of peeling of the photoresist layer or the presence or absence of plating penetration. Thereafter, the solder was immersed in a solder bath for 10 seconds under the test conditions of the solder heat resistance, and after peeling and drying, the tape was peeled off to evaluate the presence or absence of peeling of the photoresist layer. The judgment criteria are as follows.

○: There is no change at all.

△: After the plating, some infiltration was observed and the peeling of the solder after heat resistance was observed.

×: Peeling after plating.

<Electrical corrosion resistance>

Instead of using a copper foil substrate, a comb-shaped electrode B sample of IPC B-25 was used to prepare an evaluation substrate under the above conditions, and a bias voltage of DC 100 V was applied to the comb-shaped electrode to maintain a constant temperature of 85 ° C and 85% RH. The presence or absence of migration after 1,000 hours was confirmed in the wet tank. The criterion is as follows.

○: There are no changes at all.

△: Only a few changes.

×: Migration generator.

<acid resistance>

The evaluation substrate was immersed in a 10 vo1% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and the penetration or coating film dissolution was confirmed, and the peeling by tape removal was confirmed. The judgment criteria are as follows.

○: no penetration, dissolution, or peeling.

△: It was confirmed that there was little infiltration, dissolution or peeling.

×: A large amount of infiltration, dissolution or peeling was confirmed.

[Fig. 1] A diagram showing a Munsell hue ring.

Claims (13)

A photocurable resin composition which can be developed with an aqueous alkali solution, which comprises (A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, and (C) a molecule having two or more ethylenically unsaturated groups. A compound and (D) a red colorant, wherein the amount of the red colorant (D) blended is 0.05 to 3% by mass based on the total amount of the composition. The photocurable resin composition of claim 1 which further contains (E1) a blue colorant. The photocurable resin composition of claim 1 which further contains (E2) a yellow colorant. The photocurable resin composition according to any one of claims 1 to 3, wherein the color tone is blue, green, purple or orange. The photocurable resin composition of claim 1, wherein the red coloring agent (D) is a red coloring agent which does not contain any of a halogen and an azo group. The photocurable resin composition of claim 2, wherein the blue colorant (E1) is phthalocyanine blue. The photocurable resin composition of claim 1 which further contains (F) a thermosetting component. The photocurable resin composition according to any one of claims 1 to 3, wherein the coating is applied to copper. A photocurable dry film characterized in that it will be patented The photocurable resin composition according to any one of items 1 to 3 and 7 is applied to a carrier film and dried. A cured product of green, purple or orange, which is a photocurable resin composition according to any one of claims 1 to 3 and 7. A green, purple or orange hardened material which is a dry film of claim 9 of the patent application. A printed wiring board characterized by having a solder resist layer formed of a cured product of claim 10 on a substrate on which a copper circuit is formed. A printed wiring board characterized by having a solder resist layer formed of a cured product of claim 11 on a substrate on which a copper circuit is formed.