KR20200081321A - Black photosensitive resin composition - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition having excellent resolution and high hiding power due to excellent blackness and, more specifically, to a black photosensitive resin composition comprising: (A) a photosensitive resin containing a carboxyl group; (B) a photopolymerization initiator; (C) a reactive diluent; (D) an epoxy compound; and (E) a colorant, wherein the (E) colorant comprises: (E1) a phthalocyanine-based colorant; and (E2) a diketopyrrolopyrrole-based colorant.

Description

Black photosensitive resin composition

The present invention relates to a black photosensitive resin composition having excellent resolution, for example, when used as a solder resist of a printed wiring board, can cope with fine pitching and refinement of electrodes, and has excellent hiding power with excellent blackness It relates to a black photosensitive resin composition.

The printed wiring board is used to form a pattern of a conductor circuit on a substrate, and to mount electronic components on the solder land of the pattern, and circuit parts excluding the solder land are covered with an insulating protective film (for example, a solder resist film). do. In this way, when soldering electronic components to the printed wiring board, lead is prevented from adhering to unnecessary portions, and circuits (conductors) are directly exposed to the air and prevent corrosion by oxidation or humidity.

In addition, in recent years, with the advancement of technology, the demand for miniaturization and weight reduction has increased in the electronics part, and accordingly, fine pitching and miniaturization of the conductor circuit pattern of the printed wiring board in order to arrange more compact electronic components at high density. , High precision is required. Accordingly, a higher performance is required for both the insulating protective film and the resolution. In addition, a high hiding power may be required in the insulating protective film. In order to provide a high hiding power to the insulating protective film, the insulating protective film may be black.

As a material for forming a black solder resist film, a solder resist composition in which a colorant blended with a carboxyl group-containing resin is a black colorant and at least one colorant other than a black colorant has been proposed (Patent Document 1). However, since the black solder resist composition of Patent Document 1 mainly contains a black colorant as a colorant, and especially carbon black is preferably used, light absorption during exposure increases, and light tends to hardly reach the core of the solder resist coating film. There is this. Therefore, photocuring is not sufficient in the core portion of the solder resist coating film, and the size of the core portion of the solder resist coating film after development becomes small, so that the cured coating film is peeled off from the printed wiring board, so there is room for improvement in resolution.

Japanese Patent Publication No. 2008-257045

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In view of the above information, it is an object of the present invention to provide a black photosensitive resin composition having excellent resolution and high hiding power with excellent blackness.

The gist of the configuration of the present invention is as follows.

[1] It contains (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a colorant,

The black photosensitive resin composition in which the said (E) coloring agent contains (E1) phthalocyanine-type coloring agent and (E2) diketopyrrolopyrrole coloring agent.

[2] The black photosensitive resin composition according to [1], wherein the colorant (E) contains 0.20 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the photosensitive resin (A) containing a carboxyl group.

[3] The black photosensitive resin composition according to [1] or [2], containing 50 parts by mass or more and 500 parts by mass or less of the (E2) diketopyrrolopyrrole colorant based on 100 parts by mass of the phthalocyanine-based colorant (E1).

[4] The black photosensitive resin composition according to any one of [1] to [3], wherein the (E1) phthalocyanine-based colorant is phthalocyanine blue.

[5] The black photosensitive resin composition according to any one of [1] to [4], wherein the (E2) diketopyrrolopyrrole colorant is C.I.Pigment Red 264.

[6] The black photosensitive resin composition according to any one of [1] to [5], wherein the colorant (E) does not contain a black colorant.

[7] The black photosensitive resin composition according to any one of [1] to [5], wherein the colorant (E) further contains (E3) an iron oxide-based inorganic pigment.

[8] The black photosensitive resin composition according to any one of [1] to [7], wherein the colorant (E) further contains an (E4) anthraquinone colorant.

[9] The black photosensitive resin composition according to [8], wherein the (E4) anthraquinone-based colorant is chromophthal yellow.

[10] The photosensitive resin containing the carboxyl group (A),

A radically polymerizable unsaturated mono carboxylic acid is reacted with at least a part of the epoxy group of a polyfunctional epoxy resin having two or more epoxy groups in one molecule to obtain a radically polymerizable unsaturated mono carboxylic acid epoxy resin, and the resulting epoxy resin is polybasic acid Or polybasic acid-modified radical polymerizable unsaturated mono-carbon oxidized epoxy resin obtained by reacting the anhydride, and/or

A radically polymerizable unsaturated mono carboxylic acid is reacted with at least a part of the epoxy group of a polyfunctional epoxy resin having 2 or fewer epoxy groups in one molecule to obtain a radically polymerizable unsaturated mono carboxylic acid epoxy resin, and the resulting epoxy resin is a polybasic acid Alternatively, the anhydride is reacted to obtain a polybasic acid-modified radically polymerizable unsaturated mono-carbonated epoxy resin, and a part of the carboxyl group of the polybasic-modified radically polymerizable unsaturated mono-carbonated epoxy resin, and at least one radically polymerizable unsaturated group. The black photosensitive resin composition according to any one of [1] to [9], containing a polybasic acid-modified radically polymerizable unsaturated mono-carbon oxidized epoxy resin added with a radically polymerizable unsaturated group, obtained by reacting a compound having an epoxy group.

[11] A cured product obtained by photocuring the black photosensitive resin composition according to one of [1] to [10].

[12] A printed wiring board provided with a photocurable film of the black photosensitive resin composition according to any one of [1] to [10].

According to the aspect of the black photosensitive resin composition of the present invention, the colorant contains a phthalocyanine-based colorant and a diketopyrrolopyrrole-based colorant, so that photocuring sufficiently proceeds to the deep portion of the coated black photosensitive resin composition, thereby providing excellent resolution. In addition, it is also possible to obtain a cured product having a high hiding power with excellent blackness. Further, since the reduction in the width dimension of the core portion of the coating film can be prevented after development, the width dimension of the core portion of the coating film is closer to the width dimension of the surface layer portion of the coating layer, thereby improving the dimensional accuracy of the cured coating film.

According to the aspect of the black photosensitive resin composition of the present invention, by containing 50 parts by mass or more and 500 parts by mass or less of diketopyrrolopyrrole-based colorant with respect to 100 parts by mass of phthalocyanine-based colorant, excellent resolution and high hiding power can be balancedly improved. It is possible to let.

According to an aspect of the black photosensitive resin composition of the present invention, the phthalocyanine-based colorant is phthalocyanine blue, and the diketopyrrolopyrrole-based colorant is CI pigment red 264, further improving the blackness and imparting high hiding power to the cured product. It is possible.

According to the aspect of the black photosensitive resin composition of this invention, when a coloring agent does not contain a black colorant, the transmittance|permeability of the light of wavelength 300-400nm improves, and photocurability further improves to the deep part of a black photosensitive resin composition, and also, Since the black colorant does not contain carbon black, the insulating properties are improved.

Next, each component of the black photosensitive resin composition of this invention is demonstrated. The black photosensitive resin composition of the present invention contains (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a colorant, and the (E) ) The colorant contains (E-1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant.

(A) Photosensitive resin containing a carboxyl group

The chemical structure of the photosensitive resin containing a carboxyl group is not particularly limited as long as it is a resin having a photocurable property having a carboxyl group of glass. Examples of the carboxyl group-containing photosensitive resin include, for example, a resin having one or more photosensitive unsaturated double bonds. As a carboxyl group-containing photosensitive resin, more specifically, for example, when at least part of the epoxy group of a polyfunctional epoxy resin having two or more epoxy groups in one molecule is acrylic acid and/or methacrylic acid (hereinafter referred to as (meth)acrylic acid) There is. ) And a radically polymerizable unsaturated monocarboxylic acid to obtain a radically polymerizable unsaturated monocarboxylic acid epoxy resin such as epoxy (meth)acrylate, and polybasic acid obtained by reacting the resulting epoxy resin with polybasic acid or anhydride thereof It is possible to exemplify polybasic acid-modified radical polymerizable unsaturated mono-carbon oxidized epoxy resins such as modified epoxy (meth)acrylates.

The polyfunctional epoxy resin is not particularly limited as long as it is a bifunctional or higher epoxy resin. Although the epoxy equivalent of a polyfunctional epoxy resin is not specifically limited, As for the upper limit, 2000 g/eq is preferable, 1000 g/eq is more preferable, and 500 g/eq is especially preferable. On the other hand, the lower limit value of the epoxy equivalent is preferably 100 g/eq, and particularly preferably 200 g/eq.

As a polyfunctional epoxy resin, for example, cresol novolak type epoxy resins, such as o-cresol novolak type, biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin , Rubber-modified epoxy resins such as naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins and silicone-modified epoxy resins, ε-caprolactone-modified epoxy resins, phenol novolac-type epoxy resins, cyclic aliphatic polyfunctional epoxy resins, and glycidyl Ester type polyfunctional epoxy resin, glycidyl amine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol modified novolac type epoxy resin, polyfunctional modified novolac type epoxy resin, aromatic aldehyde having phenols and phenolic hydroxyl groups It is possible to exemplify a combination type epoxy resin with and the like. Moreover, you may use what introduce|transduced the halogen atom, such as Br and Cl, into such resin. These epoxy resins may be used alone or in combination of two or more. Among these, cresol novolac type epoxy resins, biphenyl aralkyl type epoxy resins, and bisphenol A type epoxy resins are preferred from the viewpoint of improving the sensitivity and resolution in a good balance.

The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, thigreen acid, angelica acid, and cinnamon acid. Of these, acrylic acid and methacrylic acid are preferred. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more.

The method of reacting the epoxy resin with the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include a method of heating the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid in a suitable diluent.

The polybasic acid or polybasic acid anhydride is reacted by addition to a hydroxyl group produced by the reaction of the epoxy resin with a radically polymerizable unsaturated monocarboxylic acid, and a carboxyl group of glass is introduced into the radically polymerizable unsaturated monocarboxylic acid epoxy resin. The polybasic acid or its anhydride is not particularly limited, and either saturated or unsaturated can be used. Polybasic acids are, for example, succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydro phthalic acid, 3-methyl tetrahydro phthalic acid, 4-methyl tetrahydro phthalic acid, 3-ethyl tetrahydro phthalic acid, 4-ethyl tetrahydro phthalic acid , Hexahydro phthalic acid, 3-methyl hexahydro phthalic acid, 4-methyl hexahydro phthalic acid, 3-ethyl hexahydro phthalic acid, 4-ethyl hexahydro phthalic acid, endo methylene tetrahydro phthalic acid, methyl endo methylene tetrahydro phthalic acid, trimellitic acid, Examples include pyromellitic acid and diglycolic acid, and examples of the polybasic acid anhydride include the anhydride of the polybasic acid. These compounds may be used alone or in combination of two or more.

In the present invention, the polybasic acid-modified unsaturated mono-carbon oxidized epoxy resin described above can also be used as a carboxyl group-containing photosensitive resin, but one or more radicals are part of the carboxyl group of the polybasic acid-modified unsaturated mono-carbon-oxidized epoxy resin obtained as described above. You may use a polybasic acid-modified radically polymerizable unsaturated mono-carbon oxidized epoxy resin obtained by addition reaction of a compound having a polymerizable unsaturated group and an epoxy group, and further adding a radically polymerizable unsaturated group. The polybasic acid-modified radically polymerizable unsaturated mono-carbonated epoxy resin to which a radically polymerizable unsaturated group is added is a polybasic acid-modified unsaturated mono-carbonated epoxy resin because a radically polymerizable unsaturated group is introduced into the polybasic-acid-modified unsaturated mono-carbonized epoxy resin. It is a carboxyl group-containing photosensitive resin with improved photosensitivity more than resin.

As a compound having at least one radically polymerizable unsaturated group and an epoxy group, it is possible to exemplify, for example, a glycidyl compound. As a glycidyl compound, for example, glycidyl acrylate, glycidyl meta acrylate, aryl glycidyl ether, penta erythritol triacrylate mono glycidyl ether, penta erythritol tri methacrylate mono glyce Dill ether and the like. Moreover, you may have multiple glycidyl groups in 1 molecule. The compounds having one or more radically polymerizable unsaturated groups and epoxy groups described above may be used alone or in combination of two or more.

Although the acid value of the carboxyl group-containing photosensitive resin is not particularly limited, the lower limit value is preferably 30 mgKOH/g, more preferably 40 mgKOH/g, and particularly preferably 50 mgKOH/g, from the viewpoint of reliable alkali development. On the other hand, the upper limit of the acid value is preferably 200 mgKOH/g from the viewpoint of preventing dissolution of the exposed portion due to alkali development, 150 mgKOH/g is more preferable from the viewpoint of preventing deterioration of the moisture resistance and electrical properties of the cured product, and 130 mgKOH/ g is particularly preferred.

The mass average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit is preferably 3000 from the viewpoint of toughness, mechanical strength, and touch dryness of the cured product, and particularly preferably 5000. On the other hand, the upper limit of the mass average molecular weight is preferably 200000, particularly preferably 50000, from the viewpoint of alkali developability.

The carboxyl group-containing photosensitive resin may be synthesized in the reaction step using the above raw materials, or the above-mentioned carboxyl group-containing photosensitive resin may be used. Examples of the carboxy group-containing photosensitive resins include, for example, SFP-4162 (Showa Denko Co., Ltd.), "JAR-20200", "JR-1121", "JL-8200", "FCC-1565" (above, Japan) Gunpowder Co., Ltd.), a resin having a chemical structure of a polybasic acid-modified unsaturated mono-carbon oxidized epoxy resin, such as "Cychroma-P (ACCA) #25" (Daicel Ornex Co., Ltd.). In addition, these carboxyl group-containing photosensitive resins may be used alone or in combination of two or more.

(B) Photopolymerization initiator

The photopolymerization initiator is not particularly limited as long as it is generally used. Specifically, for example, 1,2-octanedione, 1-[4[(phenylthio)-2-(o-benzoyl oxime)], ethanone 1-[9-ethyl-6-(2-methyl benzoyl) -9H-carbazol-3-yl]-1-(o-acetyloxime), (Z)-(9-ethyl-6-nitro-9H-carbazol-3-yl)(4-((1-me Thoxypropan-2-yl)oxy)-2-methylphenyl)methanone o-acetyl oxime, 2-(acetyl oxyimino methyl) thioxanthene-9-one, 1,8-octanedione, 1,8-bis [9-ethyl-6-nitro-9H-carbazol-3-yl]-1,8-bis(o-acetyl oxime), 1,8-octanedione, 1,8-bis[9-(2-ethyl Hexyl)-6-nitro-9H-carbazole-3-yl]-, 1,8-bis(o-acetyl oxime), (Z)-(9-ethyl-6-nitro-9H-carbazole-3- Examples include oxime ester compounds such as (4-((1-methoxy propan-2-yl)oxy)-2-methylphenyl)methanone 0-acetyl oxime. Further, acetphenone compounds such as acetphenone, dimethyl amino acetphenone, 2, 2-dimethoxy-2-phenyl acetphenone, and 2,2-diethoxy-2-phenyl acetphenone are exemplified. Moreover, as photopolymerization initiators other than the above, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, phenyl bis(2,4,6) -Trimethyl benzoyl) phosphine oxide, 2-methyl-4'-(methylthio)-2-morpholino propiophenone, 2-hydroxy-2-methyl-1-phenyl propan-1-one, 1 -Hydroxycyclohexyl phenylketone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethyl amino benzo Phenone, diclobenzophenone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amino anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-crol And thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzoyl dimethyl ketal, acetphenone dimethyl ketal, p-dimethyl amino benzoate ethyl ester, and the like. These may be used alone or in combination of two or more. Of these photopolymerization initiators, oxime ester-based compounds and acetphenone-based compounds are preferred from the viewpoint of photosensitivity.

The content of the photopolymerization initiator is not particularly limited, and is preferably 0.5 parts by mass to 30 parts by mass, and particularly preferably 1.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, hereinafter the same).

(C) reactive diluent

The reactive diluent is, for example, a photopolymerizable monomer, and is a compound having at least one polymerizable double bond per molecule, preferably at least one molecule per molecule. The reactive diluent contributes to obtaining a cured product having acid resistance, heat resistance and alkali resistance by making photocuring of the black photosensitive resin composition more sufficient.

The reactive diluent is not particularly limited as long as it is the above compound, for example, (meth)acrylic acid-2-hydroxy ethyl, phenoxy ethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, 2-hydroxy Monofunctional (meth)acrylates such as -3-phenoxy propyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, and neopentyl glycol di (Meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol adipate (meth)acrylate, hydroxy pivalic acid neopentyl glycol di(meth)acrylate, dicyclo pentanyl di(meth)acrylate , Bifunctional such as caprolactone-modified dicyclo pentenyl (meth) acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, arylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, etc. (Meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethyrol propanetri(meth)acrylate , Trifunctional (meth)acrylates such as tris(acrylic oxyethyl)isocinurate, ditrimethylol propane tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipenta erythritol hexa(meta ) (Meth)acrylate compounds, such as (meth)acrylates of 4 or more functional groups, such as acrylates and caprolactone modified dipentaerythritol hexa(meth)acrylates, urethane (meth)acrylates, etc. are mentioned. These may be used alone or in combination of two or more.

Content of a reactive diluent is not specifically limited, For example, 5.0-100 mass parts is preferable with respect to 100 mass parts of photosensitive resins containing a carboxyl group, and 10-50 mass parts is especially preferable.

(D) Epoxy compound

The epoxy compound contributes to increasing the crosslinking density of the cured product to obtain a cured product of sufficient strength. As the epoxy compound, for example, it is possible to exemplify an epoxy resin. As an epoxy resin, for example, cresol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, naphthalene type epoxy resin, dicyclo pentadiene type Rubber-modified epoxy resins such as epoxy resins and silicone-modified epoxy resins, ε-caprolactone-modified epoxy resins, phenol novolac-type epoxy resins, cyclic aliphatic polyfunctional epoxy resins, glycidyl ester-type polyfunctional epoxy resins, and glycidyl amines Bisphenol-modified novolac-type epoxy resins such as type polyfunctional epoxy resins, heterocyclic polyfunctional epoxy resins, bisphenol A novolac-type epoxy resins, polyfunctional modified novolac-type epoxy resins, epoxy resins having triazine skeletons, phenols and phenols It is possible to exemplify a combination type epoxy resin with an aromatic aldehyde having an acidic hydroxyl group. These compounds may be used alone or in combination of two or more. Of these, from the viewpoint of obtaining resolution more reliably, cresol novolac type epoxy resins, biphenyl aralkyl type epoxy resins, bisphenol-modified novolac type epoxy resins, and epoxy resins having triazine skeletons are preferred.

Content of an epoxy compound is not specifically limited, For example, 5.0-100 mass parts is preferable with respect to 100 mass parts of photosensitive resins containing a carboxyl group, and 10-50 mass parts is especially preferable.

(E) Coloring agent

As the black photosensitive resin composition of the present invention, by containing (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant as a colorant, a black color is imparted to the photosensitive resin composition. As the black photosensitive resin composition of the present invention, as the colorant, (E1) a phthalocyanine-based colorant and (E2) diketopyrrolopyrrole-based colorant, from which the photocuring proceeds sufficiently to the deep portion of the coated black photosensitive resin composition. , It is possible to obtain a cured product having excellent resolution and excellent blackness, and having high hiding power. In addition, since the photocuring proceeds sufficiently to the core portion of the coating film, it is possible to prevent a decrease in the width dimension of the core portion after development, and as a result, the width dimension of the core portion of the coating film is closer to the width dimension of the surface portion of the coating layer, thereby improving the dimensional accuracy of the cured coating layer. do.

In addition, as the black photosensitive resin composition of the present invention, any of the chromaticity index (a* value) and the chromaticity index (b* value) is near the zero value (for example, -4 to +4). Range), the redness and purpleness are suppressed, and the jetted blackness is imparted to the cured product.

Since the black photosensitive resin composition of the present invention does not need to contain a black colorant such as carbon black, the transmittance of light having a wavelength of 300 to 400 nm is improved, and the photocurability to the core of the black photosensitive resin composition is reliably improved. Moreover, since it is not necessary to contain carbon black as the black photosensitive resin composition of this invention, the insulating property of hardened|cured material improves.

(E1) Phthalocyanine Colorant

Examples of the phthalocyanine-based colorant include phthalocyanine-based pigments and phthalocyanine-based dyes. Examples of the phthalocyanine-based pigment include phthalocyanine blue pigment as a blue colorant and phthalocyanine green pigment as a green colorant. Among them, a phthalocyanine blue pigment is preferred from the viewpoint of improving the blackness of the diketopyrrolopyrrole-based colorant and suppressing the red group of the a* value of the cured product to a value close to 0 to give the cured product an eboniness. As a phthalocyanine blue pigment, for example, C.I. Pigment Blue's 1, 2, 3, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1 and the like. Of these, C.I. Pigment Blue 15:3 is preferred from the viewpoint of reliably improving the blackness and jet-blackness while obtaining high resolution.

(E2) Diketopyrrolopyrrole colorant

As the diketopyrrolopyrrole colorant, a diketopyrrolopyrrole pigment can be exemplified. As a diketopyrrolopyrrole pigment, a diketopyrrolopyrrole red pigment, a diketopyrrolopyrrole orange pigment, etc. are mentioned. Among these, diketopyrrolopyrrole-based red pigments are preferred from the viewpoint of improving the blackness together with the phthalocyanine-based colorant. As a diketopyrrolopyrrole red pigment, C.I. pigment red 254, 255, 264, 270, 272 etc. are mentioned, for example. Among them, C.I. Pigment Red 264 is preferred from the viewpoint of reliably improving the blackness while obtaining high resolution.

As the black photosensitive resin composition of the present invention, a colorant may be composed of a phthalocyanine-based colorant and a diketopyrrolopyrrole colorant, but added to a phthalocyanine-based colorant and a diketopyrrolopyrrole-based colorant, if necessary, (E3) iron oxide You may mix|blend a 2nd coloring agent, such as a system inorganic pigment and (E4) anthraquinone type coloring agent.

(E3) Iron oxide-based inorganic pigment

Examples of the iron oxide-based inorganic pigment include black iron oxide as a black colorant, yellow iron oxide as a yellow colorant, and red iron oxide as a red colorant. Of these, black iron oxide is preferred from the viewpoint of improving the blackness and resolution in a good balance with the phthalocyanine colorant and diketopyrrolopyrrole colorant.

(E4) Anthraquinone Colorant

Examples of the anthraquinone-based colorant include anthraquinone-based pigments. Examples of the anthraquinone-based pigments include anthraquinone-based yellow pigments, anthraquinone-based red pigments, and anthraquinone-based orange pigments. Among them, a phthalocyanine-based colorant and a diketopyrrolopyrrole-based colorant, together with a good balance of blackness and resolution, while suppressing the purple light closer to a value of ｂ* of the cured product more reliably by suppressing the violet light of the cured product, the blackness of the cured product is ensured. From the viewpoint of imparting, an anthraquinone-based yellow pigment is preferred. As an anthraquinone type yellow pigment, chromium phthalate yellow is especially preferable. As an anthraquinone type yellow pigment, C.I. pigment yellow-99, 123, 147, 199 etc. are mentioned, for example.

(E) The content of the colorant can be selected depending on the application conditions of the black photosensitive resin composition, and, for example, the lower limit value is a carboxyl group from the viewpoint of obtaining the blackness reliably and giving a higher hiding power to the cured product. With respect to 100 parts by mass of the photosensitive resin, 0.20 parts by mass is preferable, 0.50 parts by mass is more preferable, and 1.0 parts by mass is particularly preferable. On the other hand, the upper limit of the content of the colorant (E) is preferably 15 parts by mass, more preferably 10 parts by mass, and particularly preferably 8.0 parts by mass, from the viewpoint of imparting better resolution to the cured product.

In addition, the mixing ratio of the diketopyrrolopyrrole colorant to the phthalocyanine colorant can be selected depending on the application conditions of the black photosensitive resin composition, for example, the lower limit thereof improves the blackness and resolution of the cured product in a good balance. From the viewpoint of making it, 50 mass parts of diketopyrrolopyrrole colorant is preferable, 70 mass parts is more preferable, and 90 mass parts is particularly preferable with respect to 100 mass parts of phthalocyanine colorants. On the other hand, from the viewpoint of further improving the resolution of the cured product, the upper limit of the blending ratio of the diketopyrrolopyrrole colorant with respect to the phthalocyanine colorant is 500 parts by mass, and preferably 300 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant. It is more preferable, and 250 parts by mass is particularly preferable.

Further, in the case of blending the iron oxide-based inorganic pigment, the blending amount of the iron oxide-based inorganic pigment is preferably from 0 parts by mass to more than 0.01 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of obtaining excellent resolution. In addition, when the iron oxide-based inorganic pigment is further blended, the proportion of the iron oxide-based inorganic pigment blended with respect to the phthalocyanine-based colorant is selectable according to the application conditions of the black photosensitive resin composition, for example, the lower limit is excellent. With respect to 100 parts by mass of the phthalocyanine-based coloring agent, 1.0 parts by mass of the iron oxide-based inorganic pigment is preferable, and 1.5 parts by mass is more preferable from the viewpoint of obtaining the blackness reliably without impairing the resolution and imparting a higher silver pecking force to the cured product. And 2.0 parts by mass is particularly preferred. On the other hand, the lower limit of the blending ratio of the iron oxide-based inorganic pigment with respect to the phthalocyanine-based colorant is, from the viewpoint of reliably obtaining excellent resolution, 6.0 parts by mass is preferable, and more preferably 4.5 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant. And 3.5 parts by mass is particularly preferred.

In addition, in the case of blending an anthraquinone-based colorant, the blending ratio of the anthraquinone-based colorant to the phthalocyanine-based colorant can be selected according to the application conditions of the black photosensitive resin composition, for example, the lower limit value is excellent resolution. 50 parts by mass, preferably 100 parts by mass, and more preferably 200 parts by mass, relative to 100 parts by mass of the phthalocyanine-based colorant from the viewpoint of reliably suppressing the 기를* value of the cured product closer to 0 value without impairing the properties. Particularly preferred. On the other hand, the lower limit of the blending ratio of the anthraquinone colorant to the phthalocyanine-based colorant is preferably 800 parts by mass, more preferably 700 parts by mass, relative to 100 parts by mass of the phthalocyanine-based colorant from the viewpoint of reliably obtaining excellent resolution. , 600 parts by mass is particularly preferred.

As the black photosensitive resin composition of the present invention, it is also possible to appropriately blend various additives such as fillers, antifoaming agents, curing accelerators, and non-reactive diluents, if necessary, in addition to the above-mentioned respective components. Do.

The filler is intended to increase the physical strength of the cured product, and examples thereof include silica, barium sulfate, alumina, aluminum hydroxide, talc, and mica. As an antifoaming agent, a well-known thing can be used, For example, silicone type, hydrocarbon type, acrylic type, etc. are mentioned.

Examples of the curing accelerator include dicyandiamide (DICY) and its derivatives, organic acid hydrazide, diaminomaleonitrile (DAMN) and its derivatives, guanamine and its derivatives, melamine and its derivatives, and amineimide (AI) And the like. Moreover, as an additive, you may mix|blend dispersing agents, such as coupling agents, such as a silane type, titanate type, and alumina type, for example.

The non-reactive diluent is one that controls the dryness and coatability of the black photosensitive resin composition, and examples thereof include an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzone; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene Glycol ethers such as glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol mono methyl ether acetate, diethylene glycol mono ethyl ether acetate, and propylene glycol mono methyl ether acetate; It is possible to exemplify alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol.

The method for producing the black photosensitive resin composition described above is not limited to a specific method, but, for example, after mixing the above components in a predetermined ratio, a mill such as a three-roll roll, a bowl mill, a sand mill, or a bead mill at room temperature It is possible to manufacture by kneading, stirring, and mixing by means of kneading such as kneader, or stirring and mixing means such as a super mixer or a planetary mixer. Moreover, if necessary, you may pre-mix in the stirrer before kneading, stirring, and mixing described above.

Next, an example of a method of using the black photosensitive resin composition of the present invention will be described. Here, a method of forming an insulating protective film (for example, a solder resist film, etc.) of a printed wiring board using the black photosensitive resin composition of the present invention will be described as an example.

Screen printing method, bar coater method, blade coater method, knife coater method, on a printed wiring board which is a substrate having a circuit pattern formed by etching copper foil of the black photosensitive resin composition of the present invention obtained as described above, for example, With a roll coater method, a gravure coater method, a spray coater method, or a known coating method, a coating film is formed by coating to a desired thickness. Next, when a non-reactive diluent is contained in the black photosensitive resin composition, pre-drying is performed by heating for 15 to 60 minutes at a temperature of about 60 to 90° C. to volatilize the non-reactive diluent, and a tack-free coating film is used. To form.

Next, on the coating film, a negative film (photomask) having a pattern having a light-transmitting pattern other than the land of the circuit pattern is brought into close contact, and an active energy ray (for example, ultraviolet rays having a wavelength of 300 to 400 nm) is irradiated thereon to form the coating film. Photocuring. Then, the coating film is developed by removing the non-exposed area corresponding to the land with a dilute aqueous alkali solution. As the developing method, a spray method, a shower method, or the like is used, and examples of the dilute alkaline aqueous solution to be used include, for example, an aqueous solution of 0.5 to 5% by mass of sodium carbonate. Subsequently, it is possible to form an insulating protective film such as a solder resist film having a target pattern on the printed wiring board by performing post-cure for 20 to 80 minutes in a hot air circulation type dryer at 130 to 170°C.

[Example]

Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the spirit of the present invention is not exceeded.

Examples 1-6, Comparative Examples 1-5

Each component shown in Table 1 below was blended at the ratio shown in Table 1, and mixed and dispersed at room temperature (about 25° C.) using three rolls, and used in Examples 1-6 and Comparative Examples 1-5. A resin composition was prepared. Unless otherwise specified, the numbers in Table 1 below represent parts by mass. In addition, in Table 1 below, the blank means no compounding.

In addition, the details of each component in Table 1 are as follows.

(A) Photosensitive resin containing a carboxyl group

To 250 parts by mass of carbitol acetate, 220 parts by mass of cresol novolac-type epoxy resin (Sumimoto Chemical Industry Co., Ltd., ESCN-220, epoxy equivalent 220) and 72 parts by mass of acrylic acid were dissolved and reacted under reflux, and cresol novolac-type epoxy acrylic Rate. Subsequently, 138.6 parts by mass of hexahydro phthalic anhydride was added to the obtained cresol novolac-type epoxy acrylate, reacted under reflux until the acid value reached a theoretical value, and then reacted by adding 56.8 parts by mass of glycidyl methacrylate to react. Synthetic resin (A-1) of a photosensitive resin containing a carboxyl group of 65 mass% phosphorus (A) component was obtained.

(B) Photopolymerization initiator

ㆍNCI-８３１：ADDEA Corporation

ㆍOmnomics 　３６９: ＩＭＭＲＲｓｉｎｓ　Ｂ．Ｖ．

(C) Reactive diluent

ㆍＭｉｒａｍｅｒ　Ｍ６０：MＩＷＯＮ

ㆍＹＸ－４０００Ｋ：Mitsubishi Chemical Co., Ltd.

(D) Epoxy compound

ㆍN－65９5：DIC Corporation

ㆍＹＸ－４０００Ｋ： Mitsubishi Chemical Co., Ltd.

(E) Coloring agent

(E1) Phthalocyanine-based colorant

ㆍRionol Blue ＦＧ-73.31: Toyo Color Co., Ltd.

(E2) Diketopyrrolopyrrole colorant

ㆍＩｒｇａｚｉｎ　Ｒｕｂｉｎｅ　Ｋ　４０８５：ＢＡＳＦ社

ㆍDDP hongsr 6T：Shanghai special salt processing company

(E3) Iron oxide-based inorganic pigment

ㆍL-101: Titanium Industries Co., Ltd.

(E4) Anthraquinone colorant

ㆍChromo Phtal Yellow ABR: Chiba Specialty Chemicals Co., Ltd.

Other coloring agents

ㆍPEP－９５９NTT LACC：Toyo Color Co., Ltd.

ㆍAcetylene Black: Toyo Color Co., Ltd.

ㆍR－１４９：Liaoning Yanye dye processing company

filler

ㆍValium Sulfate Ｂ－30: Sakai Chemical Industry Co., Ltd.

Antifoam

Ｘ－５－－１０９５C： Shin-Etsu Chemical Industry Co., Ltd.

additive

ㆍMelamine: Nissan Chemical Industry Co., Ltd.

ㆍDICＹ-7: Mitsubishi Chemical Co., Ltd.

Non-reactive diluent

ㆍEDAC A：Samyang Chemical Co., Ltd.

ㆍSolvesso S-15: Ando Parachem Co., Ltd.

Test board manufacturing process

Substrate: Glass epoxy substrate (FR-4, thickness 1.6mm), conductor (Cu foil) 35μm thick Surface treatment: Buff polishing

Coating method: Screen printing DRY film thickness 20 μm

Pre-drying: 80°C, 20 minutes

Exposure: 50 mJ/cm ^{2 on the} coating film, direct line exposure machine made by Oak Corporation (wavelength 300-500 nm)

Development: 1% by mass aqueous sodium carbonate solution, 30°C, 60 seconds, spray pressure: 0.2MPa post cure: 150°C, 60 minutes

evaluation

(1) Resolution

The space from which the remaining line of the exposed portion formed with a predetermined photo magma (line width of 30 to 130 µm) was removed was visually confirmed and evaluated.

(2) Hue

With respect to the test substrate prepared as described above, according to JIS-8722, brightness (L* value), chromaticity index (a* value), and chromanetics index (b* value) were measured. As a measuring instrument, a colorimeter CM-700d (Konica Minolta Co., Ltd.) was used.

The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1 below.

[Table 1]

From Table 1, Examples 1 to 6 using a phthalocyanine-based colorant (phthalocyanine blue) and a diketopyrrolopyrrole colorant (diketopyrrolopyrrole-based red pigment) as a colorant have a resolution of 40 μm or less and excellent resolution, In addition, it is possible to obtain a photocured product having a high hiding power with a lightness (L* value) of 20 or less and excellent blackness. Further, in Examples 1 to 6, the chromaticity index (a* value) is 0.5 to 4, and the chromaticity index (b* value) is -3 to -1, whichever is near the 0 value, and to the photocured product. It is possible to impart an ebon star. In particular, in Examples 2 and 5 containing 100 to 200 parts by mass of diketopyrrolopyrrole colorant (diketopyrrolopyrrole red pigment) with respect to 100 parts by mass of phthalocyanine-based colorant (phthalocyanine blue), resolution was reduced to 30 μm. It is possible, and it is possible to obtain more excellent resolution. In addition, in Example 6 in which an epoxy resin having a triadine skeleton and a bisphenol A novolac epoxy resin were used as an epoxy compound, the resolution can be reduced to 30 μm, and more excellent resolution can be obtained. In addition, in Examples 1, 2, 4, and 6 in which an anthraquinone-based yellow pigment was blended, Example 5 and only using a phthalocyanine-based colorant (phthalocyanine blue) and a diketopyrrolopyrrole colorant (diketopyrrolopyrrole-based red pigment) By comparison, the b* value becomes closer to the 0 value, and it is possible to impart more eboniness to the photocured product.

On the other hand, neither phthalocyanine-based colorant (phthalocyanine blue) nor diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment) was used, and in Comparative Examples 1 and 3 using a carbon black-based black colorant, the resolution was 70 to 80 μm. , And it was not possible to obtain excellent resolution. In addition, although a phthalocyanine-based colorant (phthalocyanine blue) was used, a diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment) was not used, and Comparative Example 2, Comparative Example 4, and Dike using carbon black-based black colorant instead. In Comparative Example 5 using a perylene-based red colorant instead of a topyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment), the resolution was 50 to 70 μm, and it was not possible to obtain excellent resolution.

[Industrial availability]

The black photosensitive resin composition of the present invention can obtain a photocured product having excellent resolution and hiding power, and thus has high utility value in the field of an insulating film (for example, a solder resist film) coated on a printed wiring board. .

Claims (12)

(A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a colorant.
The black photosensitive resin composition containing the (E) coloring agent, (E1) a phthalocyanine-based coloring agent, and (E2) a diketopyrrolopyrrole-based coloring agent. The black photosensitive resin composition according to claim 1, wherein the colorant (E) contains 0.20 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the photosensitive resin composition containing (A) a carboxyl group. The black photosensitive resin composition according to claim 1 or 2, wherein the (E2) diketopyrrolopyrrole colorant contains 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the (E1) phthalocyanine-based colorant. The black photosensitive resin composition according to any one of claims 1 to 3, wherein the (E1) phthalocyanine-based colorant is phthalocyanine blue. The diketopyrrolopyrrole colorant (E2) according to any one of claims 1 to 4, wherein C.I. Pigment Red 264, black photosensitive resin composition. The black photosensitive resin composition according to any one of claims 1 to 5, wherein the colorant (E) does not contain a black colorant. The black photosensitive resin composition according to any one of claims 1 to 5, wherein the colorant (E) further contains (E3) an iron oxide-based inorganic pigment. The black photosensitive resin composition according to any one of claims 1 to 7, wherein the colorant (E) further contains an (E4) anthraquinone colorant. The black photosensitive resin composition according to claim 8, wherein the (E4) anthraquinone colorant is chromophthal yellow. The photosensitive resin containing the carboxyl group (A) according to any one of claims 1 to 9,
At least a part of the epoxy group of the polyfunctional epoxy resin having two or more epoxy groups in one molecule is reacted with a radically polymerizable unsaturated mono carboxylic acid to obtain a radically polymerizable unsaturated mono carbonized epoxy resin, and the resulting epoxy resin is polybasic acid or Polybasic acid-modified radical polymerizable unsaturated mono-carbon oxidized epoxy resin, which can be obtained by reacting the anhydride, and/or
At least a part of the epoxy group of the polyfunctional epoxy resin having two or more epoxy groups in one molecule is reacted with a radically polymerizable unsaturated mono carboxylic acid to obtain a radically polymerizable unsaturated mono carbonized epoxy resin, and the resulting epoxy resin is polybasic acid or The anhydride is reacted to obtain a polybasic acid-modified radically polymerizable unsaturated mono-carbon oxidized epoxy resin, and a part of the carboxyl group of the polybasic-acid-modified radically polymerizable unsaturated mono-carbonated epoxy resin is a compound having at least one radically polymerizable unsaturated group and an epoxy group. A black photosensitive resin composition containing a polybasic acid-modified radically polymerizable unsaturated mono-carbon oxidized epoxy resin to which a radically polymerizable unsaturated group is further added by reaction. A cured product obtained by photocuring the black photosensitive resin preparation according to any one of claims 1 to 10. The printed wiring board which has the photocurable film of the black photosensitive resin composition in any one of Claims 1-10.