JP2020106828A - Black photosensitive resin composition - Google Patents

Abstract

To provide a black photosensitive resin composition that has excellent resolution, excellent blackness and high hiding power.SOLUTION: A black photosensitive resin composition 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 (E) colorant containing (E1) a phthalocyanine colorant and (E2) a diketopyrrolopyrrole colorant.SELECTED DRAWING: None

Description

The present invention relates to a black photosensitive resin composition having excellent resolution, and for example, when used as a solder resist of a printed wiring board, it can correspond to fine pitch and miniaturization of electrodes and has a blackness And a black photosensitive resin composition having excellent hiding power.

A printed wiring board is used to form a conductor circuit pattern on a board and mount electronic components on the soldering lands of the pattern. Circuit parts other than the soldering lands are covered with an insulating protective film (for example, solder). (Resist film). This prevents solder from adhering to unnecessary parts when soldering electronic components to the printed wiring board, and also prevents the circuit (conductor) from being directly exposed to air and corroded by oxidation or humidity. To prevent.

Further, in recent years, with the technical progress, in the electronics field, the demand for smaller size and lighter weight has further increased, and accordingly, in order to arrange more miniaturized electronic components at high density, conductors of a printed wiring board have to be arranged. There is a demand for finer circuit patterns, finer patterns, and higher accuracy. Accordingly, the insulating protective film is also required to have higher resolution. Further, the insulating protective film may be required to have high hiding power. In order to give 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 has been proposed in which the colorant compounded in the carboxyl group-containing resin is a black colorant and one or more colorants other than the black colorant. (Patent Document 1). However, the black solder resist composition of Patent Document 1 mainly contains a black colorant as a colorant, and since carbon black is particularly preferably used, the light absorption at the time of exposure is increased, and the deep part of the solder resist coating film is exposed. It tends to be difficult for the light to reach. Therefore, the photo-curing in the deep part of the solder resist coating film is not sufficient, and the dimension of the solder resist coating film deep part becomes too small after development, and the cured coating film peels off from the printed wiring board, so there is room for improvement in resolution. was there.

JP, 2008-257045, A

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

The gist of the configuration of the present invention is as follows.
[1] 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 (E) colorant contains the (E1) phthalocyanine colorant and the (E2) diketopyrrolopyrrole colorant.
[2] The black photosensitive resin composition according to [1], which contains 0.20 parts by mass or more and 15 parts by mass or less of the colorant (E) with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). Stuff.
[3] The (E2) diketopyrrolopyrrole colorant is contained in an amount of 50 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the (E1) phthalocyanine-based colorant. Black photosensitive resin composition.
[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 (E2) diketopyrrolopyrrole colorant is C.I. I. Pigment Red 264, the black photosensitive resin composition according to any one of [1] to [4].
[6] The black photosensitive resin composition according to any one of [1] to [5], in which the (E) colorant does not contain a black colorant.
[7] The black photosensitive resin composition according to any one of [1] to [5], wherein the (E) colorant 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 (E) colorant further contains (E4) anthraquinone colorant.
[9] The black photosensitive resin composition according to [8], wherein the (E4) anthraquinone colorant is chromophthal yellow.
[10] The (A) carboxyl group-containing photosensitive resin is obtained by reacting a radically polymerizable unsaturated monocarboxylic acid with at least a part of epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups in one molecule. A polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin, which is obtained by obtaining a radically polymerizable unsaturated monocarboxylic oxide epoxy resin and reacting the generated hydroxyl group with a polybasic acid or an anhydride thereof, and/or 1 A hydroxyl group formed by reacting at least a part of the epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups in the molecule with a radically polymerizable unsaturated monocarboxylic acid epoxy resin to obtain a radically polymerizable unsaturated monocarboxylic oxide epoxy resin A polybasic acid or an anhydride thereof is reacted to obtain a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin, and a part of the carboxyl groups of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin A polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid epoxy resin further obtained by reacting a compound having one or more radically polymerizable unsaturated groups and an epoxy group with a radically polymerizable unsaturated group. The black photosensitive resin composition according to any one of [1] to [9].
[11] A cured product obtained by photo-curing the black photosensitive resin composition according to any one of [1] to [10].
[12] A printed wiring board provided with the 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, and thus photocures to a deep portion of the coated black photosensitive resin composition. Is sufficiently advanced, it is possible to obtain a cured product having excellent resolution and excellent blackness and high hiding power. Further, since it is possible to prevent the width dimension of the coating film deep portion after development from being reduced, the width dimension of the coating film deep portion approaches the width dimension of the coating film surface layer portion, and the dimensional accuracy of the cured coating film is improved.

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 the diketopyrrolopyrrole colorant with respect to 100 parts by mass of the phthalocyanine colorant, excellent resolution can be achieved. And high hiding power can be improved in a well-balanced manner.

According to the aspect of the black photosensitive resin composition of the present invention, the phthalocyanine colorant is phthalocyanine blue, and the diketopyrrolopyrrole colorant is C.I. I. Pigment Red 264 can improve the blackness and impart a high hiding power to the cured product.

According to the aspect of the black photosensitive resin composition of the present invention, since the colorant does not contain the black colorant, the transmittance of light having a wavelength of 300 to 400 nm is improved to a deep portion of the black photosensitive resin composition. The photo-curability is further improved, and since carbon black is not contained as a black colorant, the insulating property is improved.

Next, each component of the black photosensitive resin composition of the present invention will be described. The black photosensitive resin composition of the present invention comprises (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) colorant contains a (E1) phthalocyanine colorant and (E2) a diketopyrrolopyrrole colorant.

(A) Carboxyl Group-Containing Photosensitive Resin The chemical structure of the carboxyl group-containing photosensitive resin is not particularly limited as long as it is a resin having a free carboxyl group and having a photocuring property. Examples of the carboxyl group-containing photosensitive resin include resins having one or more photosensitive unsaturated double bonds. More specifically, as the carboxyl group-containing photosensitive resin, for example, acrylic acid and/or methacrylic acid (hereinafter, "(Meth)acrylic acid" may be generated) to produce a radically polymerizable unsaturated monocarboxylic acid epoxy resin such as epoxy (meth)acrylate by reaction with a radically polymerizable unsaturated monocarboxylic acid. A polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin such as a polybasic acid-modified epoxy (meth)acrylate, which is obtained by reacting the hydroxyl group with a polybasic acid or an anhydride thereof can be mentioned.

The polyfunctional epoxy resin is not particularly limited as long as it is a bifunctional or higher functional epoxy resin. The epoxy equivalent of the polyfunctional epoxy resin is not particularly limited, but the upper limit thereof is preferably 2000 g/eq, more preferably 1000 g/eq, particularly preferably 500 g/eq. On the other hand, the lower limit of the epoxy equivalent is preferably 100 g/eq, particularly preferably 200 g/eq.

Examples of the polyfunctional epoxy resin include cresol novolac type epoxy resin such as о-cresol novolac type, biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, and naphthalene type epoxy resin. , Rubber modified epoxy resin such as dicyclopentadiene type epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, phenol novolac type epoxy resin, cycloaliphatic polyfunctional epoxy resin, 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, condensate type epoxy resin of phenols and aromatic aldehyde having phenolic hydroxyl group, etc. be able to. In addition, those obtained by introducing a halogen atom such as Br or Cl into these resins may be used. These epoxy resins may be used alone or in combination of two or more. Of these, cresol novolac type epoxy resin, biphenylaralkyl type epoxy resin, and bisphenol A type epoxy resin are preferable from the viewpoint of improving the balance between sensitivity and resolution.

The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, tiglic acid, angelic acid, and cinnamic 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 and 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 added to the hydroxyl group generated by the reaction between the epoxy resin and the radical-polymerizable unsaturated monocarboxylic acid to give a free radical-polymerizable unsaturated monocarboxylic oxide epoxy resin. Carboxyl groups are introduced. The polybasic acid or its anhydride is not particularly limited, and either saturated or unsaturated can be used. Examples of the polybasic acid include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, and 4-ethyltetrahydrophthalic acid. Ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydro Examples thereof include phthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid, and examples of polybasic acid anhydrides include anhydrides of the above polybasic acids. .. These compounds may be used alone or in combination of two or more.

In the present invention, the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin described above can also be used as the carboxyl group-containing photosensitive resin, but the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin obtained as described above A polybasic acid-modified radically polymerizable unsaturated group obtained by further reacting a compound having one or more radically polymerizable unsaturated groups and an epoxy group with a part of a carboxyl group and further adding a radically polymerizable unsaturated group. Saturated monocarboxylic oxide epoxy resins may be used. The polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin further having a radically polymerizable unsaturated group is further introduced with a radically polymerizable unsaturated group in the polybasic acid modified unsaturated monocarboxylic oxide epoxy resin. Therefore, it is a carboxyl group-containing photosensitive resin having further improved photosensitivity than a polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin.

Examples of compounds having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl compounds. Examples of the glycidyl compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and pentaerythritol trimethacrylate monoglycidyl ether. In addition, you may have two or more glycidyl groups in 1 molecule. The above-mentioned compounds having one or more radically polymerizable unsaturated groups and an epoxy group may be used alone or in combination of two or more.

The acid value of the carboxyl group-containing photosensitive resin is not particularly limited, but its 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 area by the alkali developing solution, more preferably 150 mgKOH/g from the viewpoint of preventing deterioration of the humidity resistance and electric properties of the cured product, and 130 mgKOH/g. g is particularly preferred.

The weight average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit thereof is preferably 3000 from the viewpoint of toughness, mechanical strength and dryness to the touch of the cured product, and particularly preferably 5000. On the other hand, the upper limit of the mass average molecular weight is preferably 200,000, and particularly preferably 50,000 from the viewpoint of alkali developability.

The carboxyl group-containing photosensitive resin may be synthesized in the reaction step using each of the above raw materials, or may be a commercially available carboxyl group-containing photosensitive resin. Examples of commercially available carboxyl group-containing photosensitive resins include "SP-4621" (Showa Denko KK), "ZAR-2000", "ZFR-1122", "FLX-2089", and "ZCR-1569H". (Nippon Kayaku Co., Ltd.), "Cyclomer P(ACA)Z-250" (Daicel Ornex Co., Ltd.), and the like, and resins having the chemical structure of polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin You can Further, these carboxyl group-containing photosensitive resins may be used alone or in combination of two or more kinds.

(B) Photopolymerization Initiator The photopolymerization initiator is not particularly limited as long as it is commonly used. Specifically, for example, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-1-(0-acetyloxime), (Z)-(9-ethyl-6-nitro-9H-carbazol-3-yl)(4-((1-methoxypropane-2 -Yl)oxy)
2-Methylphenyl)methanone O-acetyloxime, 2-(acetyloxyiminomethyl)thioxanthen-9-one, 1,8-octanedione, 1,8-bis[9-ethyl-6-nitro-9H- Carbazol-3-yl]-,1,8-bis(O-acetyloxime),1,8-octanedione,1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazole-3 -Yl]-,1,8-bis(O-acetyloxime), (Z)
Oxime ester system such as -(9-ethyl-6-nitro-9H-carbazol-3-yl)(4-((1-methoxypropan-2-yl)oxy)-2-methylphenyl)methanone O-acetyloxime Compounds. Further, acetophenone-based compounds such as acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone can be mentioned. Further, as a photopolymerization initiator other than the above, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide , 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-(2-hydroxyethoxy) ) Phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, P-dimethylaminobenzoic acid ethyl ester Etc. These may be used alone or in combination of two or more. Among these photopolymerization initiators, oxime ester compounds and acetophenone compounds are preferable 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 1.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, hereinafter the same). Parts to 20 parts by mass are particularly preferred.

(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 two per molecule. The reactive diluent contributes to more sufficiently photocuring the black photosensitive resin composition and obtaining a cured product having acid resistance, heat resistance and alkali resistance.

The reactive diluent is not particularly limited as long as it is the above compound, and examples thereof include 2-hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, and 2-hydroxy-3. -Monofunctional (meth)acrylates such as phenoxypropyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, Bifunctional (meth)acrylates such as ethylene oxide modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth) ) Acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trifunctional (meth)acrylates such as tris(acryloxyethyl)isocyanurate, ditrimethylolpropane tetra(meth)acrylate, propion (Meth)acrylates such as acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and (meth)acrylates such as urethane (meth)acrylates ( Examples thereof include (meth)acrylate compounds. These may be used alone or in combination of two or more.

The content of the reactive diluent is not particularly limited, and for example, 5.0 to 100 parts by mass is preferable, and 10 to 50 parts by mass is particularly preferable, relative to 100 parts by mass of the carboxyl group-containing photosensitive resin.

(D) Epoxy Compound The epoxy compound contributes to increasing the crosslink density of the cured product and obtaining a cured product having sufficient strength. Examples of epoxy compounds include epoxy resins. Examples of the epoxy resin include 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, dicyclopentadiene type epoxy resin, silicone modified. Rubber modified epoxy resin such as epoxy resin, ε-caprolactone modified epoxy resin, phenol novolac type epoxy resin, cycloaliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidyl amine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin Functional epoxy resin, bisphenol-modified novolac type epoxy resin such as bisphenol A novolac type epoxy resin, polyfunctional modified novolac type epoxy resin, epoxy resin having triazine skeleton, condensate type of phenol and aromatic aldehyde having phenolic hydroxyl group An epoxy resin etc. can be mentioned. These compounds may be used alone or in combination of two or more. Of these, cresol novolac type epoxy resins, biphenylaralkyl type epoxy resins, bisphenol-modified novolac type epoxy resins, and epoxy resins having a triazine skeleton are preferable from the viewpoint of obtaining resolution more reliably.

The content of the epoxy compound is not particularly limited, and for example, 5.0 to 100 parts by mass is preferable, and 10 to 50 parts by mass is particularly preferable, relative to 100 parts by mass of the carboxyl group-containing photosensitive resin.

(E) Colorant The black photosensitive resin composition of the present invention contains (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant as a colorant, thereby making a black color a photosensitive resin. It is applied to the composition. The black photosensitive resin composition of the present invention contains (E1) a phthalocyanine-based coloring agent and (E2) a diketopyrrolopyrrole-based coloring agent as colorants, so that the coated black photosensitive resin composition can reach deep parts. Since photo-curing proceeds sufficiently, a cured product having excellent resolution and excellent blackness and high hiding power can be obtained. Further, since the photo-curing sufficiently progresses to the coating film deep portion, it is possible to prevent the reduction of the width dimension of the coating film deep portion after development, and as a result, the width dimension of the coating film deep portion approaches the width dimension of the coating film surface layer portion, and the curing The dimensional accuracy of the coating film is improved.

Further, in the black photosensitive resin composition of the present invention, both the chromanetics index (a* value) and the chromanetics index (b* value) are adjusted to near 0 value (for example, in the range of -4 to +4). As a result, redness and purpleness are suppressed, and jet-blackness is imparted to the cured product.

In the black photosensitive resin composition of the present invention, since it is not necessary 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 black photosensitive resin composition to a deep portion can be obtained. Photocurability is definitely improved. In addition, the black photosensitive resin composition of the present invention does not need to contain carbon black, so that the insulating property of the cured product is improved.

(E1) Phthalocyanine Colorant Examples of the phthalocyanine colorant include a phthalocyanine pigment and a phthalocyanine dye. Examples of the phthalocyanine-based pigment include a phthalocyanine blue pigment that is a blue colorant and a phthalocyanine green pigment that is a green colorant. Of these, the phthalocyanine blue pigment is used in combination with a diketopyrrolopyrrole colorant to improve the blackness and to bring the cured product a* value closer to 0 to suppress redness and to impart jet blackness to the cured product. preferable. Examples of the phthalocyanine blue pigment include C.I. I. Pigment Blue 1, 2, 3, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1 and the like. Among these, from the viewpoint of reliably improving blackness and jetness while obtaining high resolution, C.I. I. Pigment Blue 15:3 is preferable.

(E2) Diketopyrrolopyrrole Colorant Examples of the diketopyrrolopyrrole colorants include diketopyrrolopyrrole pigments. Examples of diketopyrrolopyrrole pigments include diketopyrrolopyrrole red pigments and diketopyrrolopyrrole orange pigments. Among these, the diketopyrrolopyrrole red pigment is preferable from the viewpoint of improving the blackness in combination with the phthalocyanine colorant. Examples of the diketopyrrolopyrrole red pigment include C.I. I. Pigment Red 254, 255, 264, 270, 272 and the like. Among these, from the viewpoint of reliably improving blackness while obtaining high resolution, C.I. I. Pigment Red 264 is preferred.

In the black photosensitive resin composition of the present invention, the colorant may be composed of a phthalocyanine colorant and a diketopyrrolopyrrole colorant, but in addition to the phthalocyanine colorant and the diketopyrrolopyrrole colorant. Then, if necessary, a second colorant such as (E3) iron oxide-based inorganic pigment and (E4) anthraquinone-based colorant may be further added.

(E3) Iron Oxide Inorganic Pigment Examples of the iron oxide inorganic pigment include black iron oxide which is a black colorant, yellow iron oxide which is a yellow colorant, and red iron oxide which is a red colorant. Of these, black iron oxide is preferable from the viewpoint of improving the blackness and the resolution in a well-balanced manner in combination with the phthalocyanine colorant and the diketopyrrolopyrrole colorant.

(E4) Anthraquinone Colorant Anthraquinone colorant may be used as the anthraquinone colorant. Examples of the anthraquinone pigment include anthraquinone yellow pigment, anthraquinone red pigment, anthraquinone orange pigment, and the like. Of these, the phthalocyanine colorant and the diketopyrrolopyrrole colorant are combined to improve the blackness and the resolution in a well-balanced manner, and the b* value of the cured product is brought closer to 0 to surely suppress the purple color. Anthraquinone-based yellow pigments are preferable from the viewpoint of surely imparting jet blackness to the cured product. As the anthraquinone yellow pigment, chromophthal yellow is particularly preferable. Examples of the anthraquinone yellow pigment include C.I. I. Pigment Yellow 99, 123, 147, 199 and the like.

The content of the (E) colorant can be selected according to the application conditions of the black photosensitive resin composition and the like. For example, the lower limit value is that the degree of blackness is reliably obtained to obtain a higher hiding power of the cured product. From the standpoint of imparting to the above, 0.20 parts by mass is preferable, 0.50 parts by mass is more preferable, and 1.0 part by mass is particularly preferable, relative to 100 parts by mass of the carboxyl group-containing photosensitive resin. On the other hand, the upper limit of the content of the (E) colorant is preferably 15 parts by mass, more preferably 10 parts by mass, and 8.0 parts by mass, from the viewpoint of imparting more excellent resolution to the cured product. Particularly preferred.

Further, the blending ratio of the diketopyrrolopyrrole colorant to the phthalocyanine colorant can be selected according to the application conditions of the black photosensitive resin composition, for example, the lower limit thereof is the blackness of the cured product. From the viewpoint of improving the resolution in a well-balanced manner, 50 parts by mass of the diketopyrrolopyrrole colorant is preferable, 70 parts by mass is more preferable, and 90 parts by mass is particularly preferable, with respect to 100 parts by mass of the phthalocyanine colorant. On the other hand, the upper limit of the mixing ratio of the diketopyrrolopyrrole colorant to the phthalocyanine colorant is 500 parts by mass with respect to 100 parts by mass of the phthalocyanine colorant from the viewpoint of further improving the resolution of the cured product. Is preferable, 300 parts by mass is more preferable, and 250 parts by mass is particularly preferable.

When an iron oxide-based inorganic pigment is further added, the content of the iron oxide-based inorganic pigment is more than 0 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of obtaining excellent resolution. It is preferably 0.01 part by mass or less. Further, when further blending the iron oxide-based inorganic pigment, the blending ratio of the iron oxide-based inorganic pigment to the phthalocyanine-based colorant can be selected according to the application conditions of the black photosensitive resin composition and the like, for example, The lower limit of the iron oxide-based inorganic pigment 1 to 100 parts by mass of the phthalocyanine-based colorant is that the blackness is surely obtained without impairing the excellent resolution and a higher hiding power is imparted to the cured product. 0.0 parts by mass is preferable, 1.5 parts by mass is more preferable, and 2.0 parts by mass is particularly preferable. On the other hand, the upper limit of the mixing ratio of the iron oxide-based inorganic pigment to the phthalocyanine-based colorant is 6.0 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant in order to reliably obtain excellent resolution. It is preferably 4.5 parts by mass, more preferably 3.5 parts by mass.

Further, in the case of further blending the 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 and the like. The value is preferably 50 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant, in order to bring the b* value of the cured product closer to a value of 0 and surely suppress purple color without impairing excellent resolution. 100 parts by mass is more preferable, and 200 parts by mass is particularly preferable. On the other hand, the upper limit of the mixing ratio of the anthraquinone colorant to the phthalocyanine colorant is preferably 800 parts by mass with respect to 100 parts by mass of the phthalocyanine colorant, from the viewpoint of reliably obtaining excellent resolution. A mass part is more preferable, and 600 mass parts is especially preferable.

In the black photosensitive resin composition of the present invention, in addition to the above-mentioned components, if necessary, various additive components, for example, various additives such as filler, defoaming agent, curing accelerator, and non-reactive diluent. Etc. can be blended appropriately.

The filler is for increasing the physical strength of the cured product, and examples thereof include silica, barium sulfate, alumina, aluminum hydroxide, talc, and mica. As the defoaming agent, known ones can be used, and examples thereof include silicone type, hydrocarbon type, and acrylic type.

Examples of the curing accelerator include dicyandiamide (DICY) and its derivative, organic acid hydrazide, diaminomaleonitrile (DAMN) and its derivative, guanamine and its derivative, melamine and its derivative, amine imide (AI) and the like. As an additive, for example, a dispersant such as a silane-based, titanate-based, or alumina-based coupling agent may be blended.

The non-reactive diluent is for adjusting the drying property 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 tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether. Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene Examples thereof include esters such as glycol monomethyl ether acetate; 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 particular method, for example, after mixing the above components in a predetermined ratio, at room temperature, three rolls, a ball mill, a sand mill, a bead mill or the like mill, a kneader. It can be produced by kneading, stirring and mixing by a kneading means such as the above, or a stirring and mixing means such as a super mixer and a planetary mixer. Moreover, you may pre-mix with a stirrer before the above-mentioned kneading|mixing, stirring, and mixing as needed.

Next, an example of how to use 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) of a printed wiring board using the black photosensitive resin composition of the present invention will be described as an example.

The black photosensitive resin composition of the present invention obtained as described above, for example, on a printed wiring board which is a substrate having a circuit pattern formed by etching a copper foil, a screen printing method, a bar coater method, a blade A coating film is formed by applying a desired thickness by a known coating method such as a coater method, a knife coater method, a roll coater method, a gravure coater method, and a spray coater method. Next, when the black photosensitive resin composition contains a non-reactive diluent, it is heated at a temperature of about 60 to 90° C. for about 15 to 60 minutes in order to volatilize the non-reactive diluent. Pre-drying is performed to form a tack-free coating film.

Next, on the coating film, a negative film (photomask) having a pattern in which parts other than the land of the circuit pattern are made transparent is brought into close contact, and active energy rays (for example, ultraviolet rays in the wavelength range of 300 to 400 nm) are applied from above. And the coating film is photocured. Then, the coating film is developed by removing the non-exposed region corresponding to the land with a dilute alkaline aqueous solution. As a developing method, a spray method, a shower method, or the like is used, and examples of the dilute alkaline aqueous solution used include a 0.5 to 5 mass% sodium carbonate aqueous solution. Then, an insulating protective film such as a solder resist film having a desired pattern can be formed on the printed wiring board by performing post-cure for 20 to 80 minutes with a hot air circulation type dryer at 130 to 170°C. it can.

Next, examples of the present invention will be described, but the present invention is not limited to these examples unless the gist thereof is exceeded.

Examples 1-6, Comparative Examples 1-5
The components shown in Table 1 below were blended in the proportions shown in Table 1 below, and mixed and dispersed at room temperature (about 25° C.) using three rolls to prepare Examples 1 to 6 and Comparative Examples 1 to 5. To prepare a black photosensitive resin composition. Unless otherwise specified, the numbers in Table 1 below are parts by mass. In addition, the blank in Table 1 below means no compounding.

The details of each component in Table 1 are as follows.
(A) Carboxyl group-containing photosensitive resin In 250 parts by mass of carbitol acetate, 220 parts by mass of cresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd., ESCN-220, epoxy equivalent 220) and 72 parts by mass of acrylic acid are dissolved, The reaction was performed under reflux to obtain a cresol novolac type epoxy acrylate. Then, to the obtained cresol novolac type epoxy acrylate, 138.6 parts by mass of hexahydrophthalic anhydride was added, reacted under reflux until the acid value reached a theoretical value, and then 56.8 parts by mass of glycidyl methacrylate was added, Further reaction was carried out to obtain a synthetic resin (A-1) of the carboxyl group-containing photosensitive resin of the component (A) having a solid content of 65% by mass.

(B) Photopolymerization Initiator/NCI-831: ADEKA Corporation
-Omnirad 369: IGM Resins B.M. V. Company

(C) Reactive diluent-Miramer M600: MIWON, YX-4000K: Mitsubishi Chemical Corporation

(D) Epoxy compound-N-695: DIC Corporation, YX-4000K: Mitsubishi Chemical Corporation

(E) Colorant (E1) Phthalocyanine-based colorant-Rionol Blue FG-7351: Toyo Color Co., Ltd. (E2) Diketopyrrolopyrrole-based colorant-Irgazin Rubine K 4085: BASF, DDP Red SR6T: Shanghai Tokushin Processing company (E3) Iron oxide inorganic pigment BL-100: Titanium Industry Co., Ltd. (E4) Anthraquinone colorant Chromophtal yellow AGR: Ciba Specialty Chemicals Co., Ltd. Other colorants PEP-959NTK BLACK: Toyo Color Co., Ltd./acetylene black: Toyo Color Co., Ltd./R-149: Liaoning Liengang dye processing company

Filler/Barium Sulfate B-30: Sakai Chemical Industry Co., Ltd. Defoaming agent X-50-1095C: Shin-Etsu Chemical Co., Ltd. Additive/Melamine: Nissan Chemical Co., Ltd./DICY-7: Mitsubishi Chemical Co., Ltd. Non-reactive dilution・EDGAC: Sanyo Kasei Co., Ltd., Solvesso S-150: Ando Parachemy Co., Ltd.

Test board manufacturing process board: glass epoxy board (FR-4, thickness 1.6 mm), conductor (Cu foil) thickness 35 μm
Substrate 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 coating film, direct drawing exposure machine made by Oak Co., Ltd. (wavelength 300 to 500 nm)
Development: 1 mass% sodium carbonate aqueous solution, 30°C, 60 seconds, spraying pressure: 0.2 MPa
Post cure: 150℃, 60 minutes

Evaluation (1) Resolution The residual line and the missing space of the exposed portion formed through a predetermined photomask (line width 30 to 130 μm) were visually confirmed and evaluated.
(2) Color Tone With respect to the test substrate prepared as described above, the lightness (L* value), the chromanetics index (a* value), and the chromanetics index (b* value) were measured according to JIS-8722. A color difference meter CM-700d (Konica Minolta Co., Ltd.) was used as a measuring instrument.

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

From Table 1 above, in Examples 1 to 6 in which a phthalocyanine colorant (phthalocyanine blue) and a diketopyrrolopyrrole colorant (diketopyrrolopyrrole red pigment) were used as the colorant, the resolution was 40 μm or less. It was possible to obtain a photo-cured product having an excellent resolution, a lightness (L* value) of 20 or less, an excellent blackness and a high hiding power. Moreover, in Examples 1 to 6, the chromanetic index (a* value) was 0.5 to 4 and the chromanetic index (b* value) was -3 to -1, which were all near 0 values, and photocured. It was possible to impart jet blackness to the object. Particularly, in Examples 2 and 5 containing 100 to 200 parts by mass of the diketopyrrolopyrrole colorant (diketopyrrolopyrrole red pigment) with respect to 100 parts by mass of the phthalocyanine colorant (phthalocyanine blue), the resolution was high. Was reduced to 30 μm, and more excellent resolution could be obtained. Further, in Example 6 in which an epoxy resin having a triazine skeleton and a bisphenol A novolac epoxy resin were used together as the epoxy compound, the resolution could be reduced to 30 μm, and more excellent resolution could be obtained. Further, in Examples 1, 2, 4, and 6 in which an anthraquinone-based yellow pigment was further added, only a phthalocyanine-based coloring agent (phthalocyanine blue) and a diketopyrrolopyrrole-based coloring agent (diketopyrrolopyrrole-based red pigment) were used. Compared to Example 5, the b* value was closer to 0, and the photocured product was able to impart jet blackness.

On the other hand, in Comparative Examples 1 and 3 using the carbon black black colorant without using the phthalocyanine colorant (phthalocyanine blue) or the diketopyrrolopyrrole colorant (diketopyrrolopyrrole red pigment), The image quality was 70 to 80 μm, and excellent resolution could not be obtained. In addition, a phthalocyanine-based coloring agent (phthalocyanine blue) was used, but a diketopyrrolopyrrole-based coloring agent (diketopyrrolopyrrole-based red pigment) was not used, and a carbon black-based black coloring agent was used instead, Comparative Example 2, In Comparative Example 4 and Comparative Example 5 in which a perylene-based red colorant was used instead of the diketopyrrolopyrrole colorant (diketopyrrolopyrrole red pigment), the resolution was 50 to 70 μm and excellent resolution was obtained. Couldn't get

The black photosensitive resin composition of the present invention can provide a photo-cured product having excellent resolution and hiding power, and therefore, for example, an insulating coating applied to a printed wiring board (eg, solder resist film). High utility value in the field of.

Claims (12)

Containing (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 (E) colorant contains the (E1) phthalocyanine colorant and the (E2) diketopyrrolopyrrole colorant. The black photosensitive resin composition according to claim 1, which contains 0.20 parts by mass or more and 15 parts by mass or less of the (E) colorant with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. The black photosensitive resin composition according to claim 1, which contains 50 parts by mass or more and 500 parts by mass or less of the (E2) diketopyrrolopyrrole colorant with respect to 100 parts by mass of the (E1) phthalocyanine colorant. Stuff. The black photosensitive resin composition according to any one of claims 1 to 3, wherein the (E1) phthalocyanine-based colorant is phthalocyanine blue. The (E2) diketopyrrolopyrrole colorant is C.I. I. Pigment Red 264, The black photosensitive resin composition according to any one of claims 1 to 4. The black photosensitive resin composition according to any one of claims 1 to 5, wherein the (E) colorant does not contain a black colorant. The black photosensitive resin composition according to claim 1, wherein the (E) colorant further contains (E3) an iron oxide-based inorganic pigment. The black photosensitive resin composition according to claim 1, wherein the (E) colorant further contains (E4) anthraquinone-based colorant. The black photosensitive resin composition according to claim 8, wherein the (E4) anthraquinone colorant is chromophthal yellow. The (A) carboxyl group-containing photosensitive resin is radically polymerizable by reacting a radically polymerizable unsaturated monocarboxylic acid with at least a part of epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups in one molecule. A polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin obtained by reacting a polybasic acid or an anhydride thereof with an unsaturated monocarboxylic oxide epoxy resin produced, and/or in one molecule At least a part of the epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups is reacted with a radical-polymerizable unsaturated monocarboxylic acid to obtain a radical-polymerizable unsaturated monocarboxylic oxide epoxy resin, and the generated hydroxyl groups are polybasic. A polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin is obtained by reacting an acid or an anhydride thereof, and a part of the carboxyl groups of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin is added to 1 Containing a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin obtained by reacting a compound having one or more radically polymerizable unsaturated groups and an epoxy group, which is further added with a radically polymerizable unsaturated group The black photosensitive resin composition according to any one of claims 1 to 9. A cured product obtained by photocuring the black photosensitive resin composition according to any one of claims 1 to 10. A printed wiring board comprising the photocurable film of the black photosensitive resin composition according to claim 1.