CN111381441A - Black photosensitive resin composition - Google Patents
Black photosensitive resin composition Download PDFInfo
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- CN111381441A CN111381441A CN201911373655.2A CN201911373655A CN111381441A CN 111381441 A CN111381441 A CN 111381441A CN 201911373655 A CN201911373655 A CN 201911373655A CN 111381441 A CN111381441 A CN 111381441A
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- colorant
- photosensitive resin
- resin composition
- black photosensitive
- epoxy resin
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
Abstract
The present invention provides a black photosensitive resin composition having excellent clarity and excellent blackness, thereby having high hiding power. The black photosensitive resin composition comprises (A) a carboxyl group-containing photosensitive resin, (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
Technical Field
The present invention relates to a black photosensitive resin composition having excellent resolution, and for example, to a black photosensitive resin composition having excellent blackness and high hiding power, which can cope with fine pitches and miniaturization of electrodes when used as a solder resist for a printed wiring board.
Background
Printed wiring boards are used to form a pattern of a conductor circuit on a substrate and mount electronic components on pads of the pattern, and circuit portions other than the pads are covered with an insulating protective film (e.g., solder resist). Thus, when electronic parts are soldered on a printed wiring board, it is possible to prevent solder from adhering to other parts where solder is not required, and to prevent a circuit (conductor) from being directly exposed to air to be oxidized or corroded by moisture.
In recent years, with the progress of technology, there has been an increasing demand for smaller and lighter electronic components in the electronic field, and accordingly, finer pitches, finer sizes, and higher accuracy of conductor circuit patterns of printed wiring boards have been demanded in order to arrange more miniaturized electronic components at higher density. Accordingly, the insulating protective film is also required to have higher performance in terms of definition. In addition, the insulating protective film is sometimes required to have high hiding power. The insulating protective film may be black to impart a high covering power.
As a material for forming a black solder resist, a solder resist composition has been proposed in which a colorant mixed in a 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 particularly preferably uses carbon black so that light absorption at the time of exposure is increased and it is difficult for light to reach deep into a solder resist coating film. Therefore, the photocuring at the depth of the solder resist coating film is insufficient, the dimension at the depth of the solder resist coating film after development becomes excessively small, and the cured coating film is peeled off from the printed wiring board, and thus there is room for improvement in the definition.
Documents of the prior art
Patent document
Patent document 1 JP 2008-257045A
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, an object of the present invention is to provide a black photosensitive resin composition having excellent clarity, excellent blackness and high hiding power.
Means for solving the problems
The gist of the configuration of the present invention is as follows.
[1] A black photosensitive resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a colorant, wherein the colorant (E) contains (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant.
[2] The black photosensitive resin composition according to [1], wherein the colorant (E) is contained in an amount of 0.20 to 15 parts by mass per 100 parts by mass of the carboxyl group-containing photosensitive resin (A).
[3] The black photosensitive resin composition according to [1] or [2], wherein the (E2) diketopyrrolopyrrole-based colorant is contained in an amount of 50 to 500 parts by mass based on 100 parts by mass of the (E1) phthalocyanine-based colorant.
[4] The black photosensitive resin composition according to any one of [1] to [3], wherein the phthalocyanine-based colorant (E1) 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 comprises an iron oxide-based inorganic pigment (E3).
[8] The black photosensitive resin composition according to any one of [1] to [7], wherein the colorant (E) further comprises an anthraquinone-based colorant (E4).
[9] The black photosensitive resin composition according to item [8], wherein the anthraquinone-based colorant (E4) is Cromophtal Yellow (Cromophtal Yellow).
[10] The black photosensitive resin composition according to any one of [1] to [9], wherein the (A) carboxyl group-containing photosensitive resin contains: a polybasic acid-modified radical-polymerizable unsaturated monocarboxylic epoxy resin and/or a polybasic acid-modified radical-polymerizable unsaturated monocarboxylic epoxy resin further added with radical-polymerizable unsaturated groups, the polybasic acid-modified radical-polymerizable unsaturated monocarboxylic epoxy resin being obtained by: a radical polymerizable unsaturated monocarboxylic acid-modified epoxy resin having 1 molecule of a polyfunctional epoxy resin having 2 or more epoxy groups is obtained by reacting at least a part of the epoxy groups of the polyfunctional epoxy resin with a radical polymerizable unsaturated monocarboxylic acid to obtain a radical polymerizable unsaturated monocarboxylic acid-modified epoxy resin, and reacting the resulting hydroxyl groups with a polybasic acid or an anhydride thereof, wherein the polybasic acid-modified radical polymerizable unsaturated monocarboxylic acid-modified epoxy resin is further added with a radical polymerizable unsaturated group, as follows: a radical polymerizable unsaturated monocarboxylic acid-based epoxy resin is obtained by reacting at least a part of epoxy groups of a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule with a radical polymerizable unsaturated monocarboxylic acid, a polybasic acid-modified radical polymerizable unsaturated monocarboxylic acid-based epoxy resin is obtained by reacting the resulting hydroxyl groups with a polybasic acid or an acid anhydride thereof, and then a part of carboxyl groups of the polybasic acid-modified radical polymerizable unsaturated monocarboxylic acid-based epoxy resin is reacted with a compound having 1 or more radical polymerizable unsaturated groups and epoxy groups.
[11] A cured product obtained by photocuring the black photosensitive resin composition according to any one of [1] to [10 ].
[12] A printed wiring board comprising a photocurable film of the black photosensitive resin composition according to any one of [1] to [10 ].
Effects of the invention
According to the form of the black photosensitive resin composition of the present invention, the colorant contains the phthalocyanine-based colorant and the diketopyrrolopyrrole-based colorant, and thus, photocuring is sufficiently performed to the depth of the black photosensitive resin composition to be applied, and a cured product having excellent resolution, excellent blackness, and high hiding power can be obtained. Further, the width dimension of the coating film at the depth after development can be prevented from decreasing, the width dimension of the coating film at the depth becomes close to the width dimension of the surface layer portion of the coating film, and the dimensional accuracy of the cured coating film can be improved.
According to the form of the black photosensitive resin composition of the present invention, the diketopyrrolopyrrole-based colorant is contained in an amount of 50 to 500 parts by mass based on 100 parts by mass of the phthalocyanine-based colorant, whereby excellent resolution and high hiding power can be improved in a well-balanced manner.
According to the form of the black photosensitive resin composition of the present invention, the phthalocyanine-based colorant is phthalocyanine blue, and the diketopyrrolopyrrole-based colorant is c.i. pigment red 264, whereby the blackness can be further improved, and a high hiding power can be imparted to the cured product.
According to the form of the black photosensitive resin composition of the present invention, since the colorant does not contain a black colorant, the transmittance of light having a wavelength of 300 to 400nm is improved, the photocurability in the depth of the black photosensitive resin composition is further improved, and the insulation property is improved because carbon black is not contained as a black colorant.
Detailed Description
Next, the respective components 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, wherein the colorant (E) contains (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based 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 photocurable resin having a free carboxyl group. Examples of the carboxyl group-containing photosensitive resin include resins having 1 or more photosensitive unsaturated double bonds. More specifically, examples of the carboxyl group-containing photosensitive resin include a polybasic acid-modified radical-polymerizable unsaturated monocarboxylic acid epoxy resin such as a polybasic acid-modified epoxy (meth) acrylate obtained by reacting at least a part of epoxy groups of a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule with a radical-polymerizable unsaturated monocarboxylic acid such as acrylic acid and/or methacrylic acid (hereinafter sometimes referred to as "(meth) acrylic acid") to obtain a radical-polymerizable unsaturated monocarboxylic acid epoxy resin such as an epoxy (meth) acrylate, and reacting the resulting hydroxyl groups with a polybasic acid or an anhydride thereof.
The polyfunctional epoxy resin is not particularly limited, and may be any epoxy resin having 2 or more functions. The epoxy equivalent of the polyfunctional epoxy resin is not particularly limited, and the upper limit thereof is preferably 2000g/eq, more preferably 1000g/eq, and particularly preferably 500 g/eq. On the other hand, the lower limit of the epoxy equivalent is preferably 100g/eq, and particularly preferably 200 g/eq.
Examples of the polyfunctional epoxy resin include: an epoxy resin modified with rubber such as cresol novolak type epoxy resin 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, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, silicone modified epoxy resin, epsilon-caprolactone modified epoxy resin, novolak type epoxy resin, alicyclic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidylamine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol modified novolak type epoxy resin, polyfunctional modified novolak type epoxy resin, and a condensate type epoxy resin of phenol and aromatic aldehyde having a phenolic hydroxyl group. Further, a halogen atom such as Br or Cl may be introduced into the resin and then used. The epoxy resins may be used alone or in combination of two or more. Among them, cresol novolac type epoxy resins, biphenyl aralkyl type epoxy resins, and bisphenol a type epoxy resins are preferably used from the viewpoint of improving sensitivity and resolution in a well-balanced manner.
The radical polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, tiglic acid (tiglic acid), angelic acid, cinnamic acid, and the like. Among them, acrylic acid and methacrylic acid are preferable. The radical polymerizable unsaturated monocarboxylic acid 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 an appropriate diluent.
The polybasic acid or polybasic acid anhydride is subjected to addition reaction with the hydroxyl group formed by the reaction of the epoxy resin and the radical polymerizable unsaturated monocarboxylic acid, thereby introducing a free carboxyl group into the radical polymerizable unsaturated monocarboxylic acid-based epoxy resin. The polybasic acid or anhydride thereof is not particularly limited, and a saturated or unsaturated polybasic acid or anhydride thereof can be used. Examples of the polybasic acids include: succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid, and diglycolic acid. These compounds may be used alone or in combination of two or more.
In the present invention, the polybasic acid-modified unsaturated monocarboxylic acid-based epoxy resin may be used as the carboxyl group-containing photosensitive resin, and a polybasic acid-modified radical-polymerizable unsaturated monocarboxylic acid-based epoxy resin obtained by addition reaction of a part of the carboxyl groups of the polybasic acid-modified unsaturated monocarboxylic acid-based epoxy resin obtained as described above and a compound having 1 or more radical-polymerizable unsaturated groups and epoxy groups may be used as the further radical-polymerizable unsaturated group. The polybasic acid-modified radical-polymerizable unsaturated monocarboxylic acid-based epoxy resin to which a radical-polymerizable unsaturated group is further added has a radical-polymerizable unsaturated group introduced into the polybasic acid-modified unsaturated monocarboxylic acid-based epoxy resin, and therefore, the photosensitivity is further improved as compared with the polybasic acid-modified unsaturated monocarboxylic acid-based epoxy resin.
Examples of the compound having 1 or more radical polymerizable unsaturated groups and epoxy groups include glycidyl compounds. Examples of the glycidyl compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythritol trimethacrylate monoglycidyl ether, and the like. In addition, 1 molecule may contain a plurality of glycidyl groups. The above-mentioned compounds having 1 or more radical polymerizable unsaturated groups and epoxy groups may be used alone or two or more kinds may be used simultaneously.
The acid value of the carboxyl group-containing photosensitive resin is not particularly limited, and from the viewpoint of reliably carrying out alkali development, the lower limit thereof is preferably 30mgKOH/g, more preferably 40mgKOH/g, and particularly preferably 50 mgKOH/g. On the other hand, the upper limit of the acid value is preferably 200mgKOH/g from the viewpoint of preventing the alkali developing solution from dissolving the exposed portion, and more preferably 150mgKOH/g, and particularly preferably 130mgKOH/g from the viewpoint of preventing the cured product from deteriorating in moisture resistance and electrical characteristics.
The mass average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, and the lower limit is preferably 3000, and particularly preferably 5000, from the viewpoint of toughness, mechanical strength and touch drying property of the cured product. On the other hand, from the viewpoint of alkali developability, the upper limit of the mass average molecular weight is preferably 200000, and particularly preferably 50000.
The carboxyl group-containing photosensitive resin may be a resin synthesized by the above reaction procedure using the above raw materials, or a commercially available carboxyl group-containing photosensitive resin may be used. Examples of commercially available carboxyl group-containing photosensitive resins include resins having a chemical structure of a polybasic acid-modified unsaturated monocarboxylic acid-based epoxy resin such as "SP-4621" (Showa Denko K.K.), "ZAR-2000", "ZFR-1122", "FLX-2089", "ZCR-1569H" (manufactured by Nippon Kagaku K.K.), "Cyclomer P (ACA) Z-250" (Daicel Ornex K.K.). 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, and a general photopolymerization initiator may be used. Specific examples thereof include: 1, 2-octanedione, 1- [ 4- (phenylthio) -2- (O-benzoyloxime) ], ethanone 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), (Z) - (9-ethyl-6-nitro-9H-carbazol-3-yl) (4- ((1-methoxypropan-2-yl) oxy) -2-methylphenyl) methanone O-acetyloxime, 2- (acetoxyiminomethyl) thioxanthone-9-one, 1, 8-octanedione, 1, 8-bis [ 9-ethyl-6-nitro-9H-carbazol-3-yl ] -, oxime ester compounds such as 1, 8-bis (O-acetyloxime), 1, 8-octanedione, 1, 8-bis [9- (2-ethylhexyl) -6-nitro-9H-carbazol-3-yl ] -,1, 8-bis (O-acetyloxime), and (Z) - (9-ethyl-6-nitro-9H-carbazol-3-yl) (4- ((1-methoxypropan-2-yl) oxy) -2-methylphenyl) methanone O-acetyloxime. Further, there may be mentioned: acetophenone compounds such as acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, and 2, 2-diethoxy-2-phenylacetophenone. Further, examples of the photopolymerization initiator other than the above include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-4 '- (methylthio) -2-morpholinylphenylethyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenyl benzophenone, 4' -diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, methyl-thioxanthone, methyl-ethyl-phenyl ether, methyl-butyl ether, phenyl-2-, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, ethyl p-dimethylaminobenzoate, and the like. These photopolymerization initiators 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 to 30 parts by mass, and particularly preferably 1.0 to 20 parts by mass, relative to 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, the same applies hereinafter).
(C) Reactive diluents
The reactive diluent is a compound having at least 1, preferably at least 2, polymerizable double bonds in 1 molecule, such as a photopolymerizable monomer. The reactive diluent allows the black photosensitive resin composition to be more sufficiently photocured, and contributes to 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-mentioned compound, and examples thereof include: monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-functional (meth) acrylates such as 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, dicyclopentyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, and isocyanurate di (meth) acrylate; 3-functional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate; 4 or more functional (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate; and (meth) acrylate compounds such as urethane (meth) acrylates. These compounds may be used alone or in combination of two or more.
The content of the reactive diluent is not particularly limited, and is, for example, preferably 5.0 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing photosensitive resin.
(D) Epoxy compound
The epoxy compound contributes to increase of the crosslinking density of the cured product to obtain a cured product having sufficient strength. Examples of the epoxy compound include epoxy resins. Examples of the epoxy resin include: a rubber-modified epoxy resin such as a cresol novolak-type epoxy resin, a biphenyl aralkyl-type epoxy resin, a phenyl aralkyl-type epoxy resin, a biphenyl-type epoxy resin, a bisphenol a-type epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, a silicone-modified epoxy resin, an epsilon-caprolactone-modified epoxy resin, a novolak-type epoxy resin, an alicyclic polyfunctional epoxy resin, a glycidyl ester-type polyfunctional epoxy resin, a glycidylamine-type polyfunctional epoxy resin, a heterocyclic polyfunctional epoxy resin, a bisphenol a novolak-type epoxy resin, a polyfunctional modified novolak-type epoxy resin, an epoxy resin having a triazine skeleton, a condensate-type epoxy resin of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, and the like. These compounds may be used alone or in combination of two or more. Among them, cresol novolak type epoxy resins, biphenyl aralkyl type epoxy resins, bisphenol modified novolak type epoxy resins, and epoxy resins having a triazine skeleton are preferable from the viewpoint of more reliably obtaining definition.
The content of the epoxy compound is not particularly limited, and is, for example, preferably 5.0 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing photosensitive resin.
(E) Coloring agent
The black photosensitive resin composition of the present invention contains (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant as colorants to impart a black hue to the photosensitive resin composition. The black photosensitive resin composition of the present invention contains the phthalocyanine-based colorant (E1) and the diketopyrrolopyrrole-based colorant (E2) as the colorants, and thus photocuring proceeds sufficiently to the deep part of the black photosensitive resin composition to be coated, and therefore, a cured product having excellent resolution, excellent blackness, and high hiding power can be obtained. Further, since the depth of the coating film is sufficiently photocured, the width dimension of the coating film at the depth after development can be prevented from decreasing, and as a result, the width dimension of the coating film at the depth approaches the width dimension of the surface layer portion of the coating film, and the dimensional accuracy of the cured coating film is improved.
In the black photosensitive resin composition of the present invention, both the color index (a value) and the color index (b value) can be adjusted to values close to 0 (for example, in the range of-4 to + 4), whereby red and violet can be suppressed, and a jet-black property can be imparted to a cured product.
Since the black photosensitive resin composition of the present invention does not need to contain a black coloring agent such as carbon black, the transmittance of light having a wavelength of 300 to 400nm is improved, and the photocurability in the deep part of the black photosensitive resin composition is surely improved. In addition, since the black photosensitive resin composition of the present invention does not need to contain carbon black, the insulating properties of the cured product are improved.
(E1) Phthalocyanine-based colorant
Examples of the phthalocyanine-based colorant include phthalocyanine-based pigments and phthalocyanine-based dyes. Examples of the phthalocyanine pigment include a phthalocyanine blue pigment as a blue colorant and a phthalocyanine green pigment as a green colorant. Among them, phthalocyanine blue pigments are preferable in that they act together with diketopyrrolopyrrole-based colorants to increase the blackness, make the a value of the cured product close to 0, and suppress the red color to impart a jet-black property to the cured product. Examples of the phthalocyanine blue pigment include c.i. pigment blue 1,2, 3, 15: 1. 15: 2. 15: 3. 15: 4. 15: 5. 15: 6. 16, 17: 1, etc. Among them, from the viewpoint of obtaining high definition while reliably improving blackness and jet-blackness, c.i. pigment blue 15: 3.
(E2) diketopyrrolopyrrole-based coloring agents
Examples of the diketopyrrolopyrrole-based colorant include diketopyrrolopyrrole-based pigments. Examples of the diketopyrrolopyrrole-based pigment include a diketopyrrolopyrrole-based red pigment and a diketopyrrolopyrrole-based orange pigment. Among them, from the viewpoint of improving the blackness by cooperating with the phthalocyanine-based colorant, the diketopyrrolopyrrole-based red pigment is preferable. Examples of the diketopyrrolopyrrole-based red pigment include c.i. pigment red 254, 255, 264, 270 and 272. Among them, c.i. pigment red 264 is preferable from the viewpoint of obtaining high definition and reliably improving blackness.
In the black photosensitive resin composition of the present invention, the colorant includes a phthalocyanine-based colorant and a diketopyrrolopyrrole-based colorant, but the 2 nd colorant such as (E3) an iron oxide-based inorganic pigment and (E4) an anthraquinone-based colorant may be further added as necessary in addition to the phthalocyanine-based colorant and the diketopyrrolopyrrole-based colorant.
(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. Among them, black iron oxide is preferable in terms of improving the balance between blackness and sharpness by cooperating with a phthalocyanine-based colorant and a diketopyrrolopyrrole-based colorant.
(E4) Anthraquinone-based colorant
Anthraquinone pigments are exemplified as the anthraquinone colorants. Examples of the anthraquinone-based pigment include an anthraquinone-based yellow pigment, an anthraquinone-based red pigment, and an anthraquinone-based orange pigment. Among these, anthraquinone yellow pigments are preferable in that they can improve the blackness and sharpness in a well-balanced manner by cooperating with phthalocyanine colorants and diketopyrrolopyrrole colorants, and can reliably suppress the violet color by making the b-value of the cured product close to 0, thereby reliably imparting the blackness to the cured product. The anthraquinone-based yellow pigment is preferably kromovor yellow. Examples of the anthraquinone yellow pigment include c.i. pigment yellow 99, 123, 147, 199, and the like.
(E) The content of the colorant is appropriately selected depending on the application conditions of the black photosensitive resin composition, and for example, from the viewpoint of reliably obtaining the blackness and imparting a higher hiding power to the cured product, the lower limit value thereof is preferably 0.20 parts by mass, more preferably 0.50 parts by mass, and particularly preferably 1.0 part by mass with respect 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 particularly preferably 8.0 parts by mass, from the viewpoint of imparting more excellent definition to the cured product.
The addition ratio of the diketopyrrolopyrrole-based colorant to the phthalocyanine-based colorant may be appropriately selected depending on the application conditions of the black photosensitive resin composition and the like, and for example, from the viewpoint of improving the blackness and the clarity of a cured product in a well-balanced manner, the lower limit of the diketopyrrolopyrrole-based colorant is preferably 50 parts by mass, more preferably 70 parts by mass, and particularly preferably 90 parts by mass, based on 100 parts by mass of the phthalocyanine-based colorant. On the other hand, the upper limit of the addition ratio of the diketopyrrolopyrrole-based colorant to the phthalocyanine-based colorant is preferably 500 parts by mass, more preferably 300 parts by mass, and particularly preferably 250 parts by mass, per 100 parts by mass of the phthalocyanine-based colorant, from the viewpoint of further improving the resolution of a cured product.
In addition, when the iron oxide-based inorganic pigment is further added, the content of the iron oxide-based inorganic pigment is preferably more than 0 part by mass and 0.01 part by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of obtaining excellent definition. When the iron oxide-based inorganic pigment is further added, the addition ratio of the iron oxide-based inorganic pigment to the phthalocyanine-based colorant may be appropriately selected depending on the application conditions of the black photosensitive resin composition and the like, and for example, from the viewpoint of reliably obtaining blackness without impairing excellent clarity and imparting higher hiding power to a cured product, the lower limit value of the iron oxide-based inorganic pigment is preferably 1.0 part by mass, more preferably 1.5 parts by mass, and particularly preferably 2.0 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant. On the other hand, from the viewpoint of reliably obtaining excellent resolution, the upper limit of the addition ratio of the iron oxide-based inorganic pigment to the phthalocyanine-based colorant is preferably 6.0 parts by mass, more preferably 4.5 parts by mass, and particularly preferably 3.5 parts by mass, relative to 100 parts by mass of the phthalocyanine-based colorant.
When the anthraquinone-based colorant is further added, the proportion of the anthraquinone-based colorant to the phthalocyanine-based colorant may be appropriately selected depending on the application conditions of the black photosensitive resin composition, and for example, from the viewpoint of reliably bringing the b x value of the cured product closer to 0 without impairing excellent clarity to suppress violet, the lower limit value thereof is preferably 50 parts by mass, more preferably 100 parts by mass, and particularly preferably 200 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant. On the other hand, from the viewpoint of reliably obtaining excellent resolution, the upper limit of the addition ratio of the anthraquinone-based colorant to the phthalocyanine-based colorant is preferably 800 parts by mass, more preferably 700 parts by mass, and particularly preferably 600 parts by mass with respect to 100 parts by mass of the phthalocyanine-based colorant.
In addition to the above components, various components, for example, various additives such as a filler, a defoaming agent, and a curing accelerator, a non-reactive diluent, and the like may be added to the black photosensitive resin composition of the present invention as appropriate.
The filler is used for improving the physical strength of the cured product, and examples thereof include silica, barium sulfate, alumina, aluminum hydroxide, talc, mica, and the like. As the defoaming agent, known ones can be used, and examples thereof include silicone defoaming agents, hydrocarbon defoaming agents, and acrylic defoaming agents.
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 Aminimide (AI). Further, as the additive, for example, a silane-based, titanate-based, alumina-based coupling agent may be added.
The non-reactive diluent is used for adjusting the drying property and the coating property 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; glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol.
The method for producing the black photosensitive resin composition is not limited to a specific method, and for example, the black photosensitive resin composition can be produced by mixing the above components at a predetermined ratio, and then kneading, stirring, and mixing the mixture at room temperature using a mill such as a three-roll mill, a ball mill, a sand mill, or a bead mill, a kneading device such as a kneader, or a stirring/mixing device such as a super mixer or a planetary mixer. Further, the above-mentioned kneading, stirring and mixing may be preceded by premixing with a stirrer as required.
Next, an example of a method for using the black photosensitive resin composition of the present invention will be described. The method of forming an insulating protective film (e.g., solder resist) for 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 is applied to a printed wiring board, which is a substrate having a circuit pattern formed by etching a copper foil, by a known coating method such as screen printing, bar coating, blade coating, roll coating, gravure coating, or spray coating, in a desired thickness to form a coating film. Next, when the black photosensitive resin composition contains a non-reactive diluent, it is pre-dried and heated at about 60 to 90 ℃ for 15 to 60 minutes to volatilize the non-reactive diluent, thereby forming a non-tacky coating film.
Then, a negative film (photomask) having a pattern for transmitting light to the region other than the land of the circuit pattern is adhered to the coating film, and an active energy ray (for example, ultraviolet ray having a wavelength of 300 to 400 nm) is irradiated thereon to photocure the coating film. Then, the non-exposed region corresponding to the pad is removed with a dilute alkaline aqueous solution to develop the coating film. The developing method uses a spray method, a shower method, or the like, and the used dilute alkaline aqueous solution includes, for example, a 0.5 to 5 mass% sodium carbonate aqueous solution. Then, a post-curing is performed at 130 to 170 ℃ for 20 to 80 minutes by a hot air circulation dryer or the like, whereby an insulating protective film such as a solder resist having a target pattern can be formed on the printed wiring board.
Examples
Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist is not exceeded.
Examples 1 to 6 and comparative examples 1 to 5
The black photosensitive resin compositions used in examples 1 to 6 and comparative examples 1 to 5 were prepared by adding the components shown in Table 1 at the ratios shown in Table 1 below, and mixing and dispersing the components at room temperature (about 25 ℃ C.) using a three-roll mill. Unless otherwise specified, the numbers in table 1 below represent parts by mass. In addition, the blank column in table 1 below indicates no addition.
In addition, each component in table 1 is described in detail below.
(A) Carboxyl group-containing photosensitive resin
In 250 parts by mass of carbitol acetate, 220 parts by mass of cresol novolak type epoxy resin (sumitomo chemical industries co., ltd., ESCN-220, epoxy equivalent 220) and 72 parts by mass of acrylic acid were dissolved and reacted under reflux to obtain cresol novolak type epoxy acrylate. Then, 138.6 parts by mass of hexahydrophthalic anhydride was added to the obtained cresol novolak type epoxy acrylate, and after the reaction was carried out under reflux until the acid value reached the theoretical value, 56.8 parts by mass of glycidyl methacrylate was added, and the reaction was further carried out, thereby obtaining a synthetic resin (a-1) which is a carboxyl group-containing photosensitive resin as a component (a) having a solid content of 65 mass%.
(B) Photopolymerization initiator
NCI-831: ADEKA, Inc
Omnirad 369: IGM Resins B.V. Co
(C) Reactive diluents
Miramer M600: MIWON Corp
YX-4000K: mitsubishi chemical corporation
(D) Epoxy compound
N-695: DIC corporation
YX-4000K: mitsubishi chemical corporation
(E) Coloring agent
(E1) Phthalocyanine-based colorant
Raonol Blue (Lionol Blue) FG-7351: toyo color Co Ltd
(E2) Diketopyrrolopyrrole-based coloring agents
Irgazin Rubine K4085: BASF Corp Ltd
DDP Red SR 6T: shanghai Special gloss processing Co Ltd
(E3) Iron oxide-based inorganic pigment
BL-100: titanium industries Co Ltd
(E4) Anthraquinone-based colorant
Claumo taer yellow AGR: ciba Jing corporation
Other colorants
PEP-959NTK BLACK: toyo color Co Ltd
Acetylene black: toyo color Co Ltd
R-149: liaoning Lingang dyestuff chemical Co Ltd
Filler material
Barium sulfate B-30: sakai chemical industry Co., Ltd
Defoaming agent
X-50-1095C: shin-Etsu chemical industry Co
Additive agent
Melamine: nissan chemical industry Co., Ltd
DICY-7: mitsubishi chemical corporation
Non-reactive diluents
EDGAC: sanyan finished product corporation
Solvesso S-150: andeng PARACHEMIE Kabushiki Kaisha
Test substrate manufacturing process
Substrate: glass epoxy substrate (FR-4, thickness 1.6mm) and conductor (Cu foil) thickness 35 μm
Substrate surface treatment: polishing of
The coating method comprises the following steps: DRY film thickness of 20 μm for screen printing
Pre-drying: 80 ℃ for 20 minutes
Exposure: 50mJ/cm on the coating film2Direct-write exposure machine (wavelength 300 to 500nm) manufactured by Oak corporation
And (3) developing: 1 mass% sodium carbonate aqueous solution, 30 ℃, 60 seconds, spray pressure: 0.2MPa
Post-curing: 150 ℃ for 60 minutes
Evaluation of
(1) Definition of
The residual lines and spaces of the exposed portions formed by a predetermined photomask (line width 30 to 130 μm) were visually checked and evaluated.
(2) Color tone
For the test substrates prepared as described above, the brightness (L value), the color index (a value), and the color index (b value) were measured according to JIS-8722. The measurement apparatus used was a color difference meter CM-700d (Konika Meinenda Co., Ltd.).
The evaluation results of examples 1 to 6 and comparative examples 1 to 5 are shown in Table 1 below.
[ Table 1]
According to table 1 above, in examples 1 to 6 using a phthalocyanine-based colorant (phthalocyanine blue) and a diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment) as the colorants, photocured products having a resolution of 40 μm or less and excellent resolution, and a luminance (L value) of 20 or less and excellent blackness and having a high hiding power were obtained. In examples 1 to 6, the color index (a) was 0.5 to 4, and the color index (b) was-3 to-1, both values being close to 0, and the photo-cured product was provided with a jet-black property. In particular, in examples 2 and 5 in which 100 to 200 parts by mass of a diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment) was contained per 100 parts by mass of a phthalocyanine-based colorant (phthalocyanine blue), the resolution was as low as 30 μm, and more excellent resolution was obtained. Further, in example 6 in which an epoxy resin having a triazine skeleton and a bisphenol a novolac epoxy resin are used together as an epoxy compound, the resolution can be as low as 30 μm, so that more excellent resolution can be obtained. In addition, in examples 1,2, 4 and 6 in which an anthraquinone-based yellow pigment was further added, the b value was closer to 0 value than in example 5 in which only a phthalocyanine-based colorant (phthalocyanine blue) and a diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment) were used, and thus, the photo-cured product could be further provided with a jet-black property.
On the other hand, in comparative examples 1 and 3 in which a carbon black-based black colorant was used instead of a phthalocyanine-based colorant (phthalocyanine blue) and a diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment), the resolution was 70 to 80 μm, and excellent resolution could not be obtained. In addition, in comparative examples 2 and 4 in which a phthalocyanine-based colorant (phthalocyanine blue) was used and a carbon black-based black colorant was used instead of the diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment), and comparative example 5 in which a perylene-based red colorant was used instead of the diketopyrrolopyrrole-based colorant (diketopyrrolopyrrole-based red pigment), the resolution was 50 to 70 μm, and excellent resolution could not be obtained.
Industrial applicability of the invention
The black photosensitive resin composition of the present invention can give a photocured product having excellent definition and hiding power, and therefore has a high utility value in the field of, for example, an insulating film (e.g., a solder resist) applied to a printed wiring board.
Claims (12)
1. A black photosensitive resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a colorant,
the colorant (E) contains (E1) a phthalocyanine-based colorant and (E2) a diketopyrrolopyrrole-based colorant.
2. The black photosensitive resin composition according to claim 1, wherein the colorant (E) is contained in an amount of 0.20 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin (A).
3. The black photosensitive resin composition according to claim 1 or 2, wherein the (E2) diketopyrrolopyrrole-based 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.
4. The black photosensitive resin composition according to any one of claims 1 to 3, wherein the phthalocyanine-based colorant (E1) is phthalocyanine blue.
5. The black photosensitive resin composition according to any one of claims 1 to 4, wherein the (E2) diketopyrrolopyrrole-based colorant is C.I. pigment Red 264.
6. The black photosensitive resin composition according to any one of claims 1 to 5, wherein the colorant (E) does not contain a black colorant.
7. The black photosensitive resin composition according to any one of claims 1 to 5, wherein the colorant (E) further comprises an iron oxide-based inorganic pigment (E3).
8. The black photosensitive resin composition according to any one of claims 1 to 7, wherein the colorant (E) further comprises an anthraquinone-based colorant (E4).
9. The black photosensitive resin composition according to claim 8, wherein the anthraquinone-based colorant (E4) is Kromofuta yellow.
10. The black photosensitive resin composition according to any one of claims 1 to 9, wherein the carboxyl group-containing photosensitive resin (A) contains a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid-based epoxy resin obtained by reacting at least a part of epoxy groups of a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule with a radically polymerizable unsaturated monocarboxylic acid to obtain a radically polymerizable unsaturated monocarboxylic acid-based epoxy resin and reacting the resulting hydroxyl groups with a polybasic acid or an anhydride thereof, and/or a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid-based epoxy resin further having 2 or more epoxy groups in 1 molecule to obtain a radically polymerizable unsaturated monocarboxylic acid-based epoxy resin The epoxy resin composition is obtained by reacting at least a part of epoxy groups of an epoxy resin with a radical polymerizable unsaturated monocarboxylic acid to obtain a radical polymerizable unsaturated monocarboxylic acid epoxy resin, reacting the resulting hydroxyl groups with a polybasic acid or an anhydride thereof to obtain a polybasic acid-modified radical polymerizable unsaturated monocarboxylic acid epoxy resin, and then reacting a part of carboxyl groups of the polybasic acid-modified radical polymerizable unsaturated monocarboxylic acid epoxy resin with a compound having 1 or more radical polymerizable unsaturated groups and epoxy groups.
11. A cured product obtained by photocuring the black photosensitive resin composition according to any one of claims 1 to 10.
12. A printed wiring board comprising a photocurable film of the black photosensitive resin composition according to any one of claims 1 to 10.
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| JP2018243964 | 2018-12-27 | ||
| JP2018-243964 | 2018-12-27 | ||
| JP2019214348A JP6843949B2 (en) | 2018-12-27 | 2019-11-27 | Black photosensitive resin composition |
| JP2019-214348 | 2019-11-27 |
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| CN112711175A (en) * | 2021-01-28 | 2021-04-27 | 杭州福斯特应用材料股份有限公司 | Black curable resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281368A (en) * | 2007-04-06 | 2008-10-08 | 太阳油墨制造株式会社 | Black solder resist compound and cured product thereof |
| JP2010091876A (en) * | 2008-10-09 | 2010-04-22 | Taiyo Ink Mfg Ltd | Black solder resist composition and cured material thereof |
| CN103676476A (en) * | 2012-09-05 | 2014-03-26 | 株式会社田村制作所 | Black solidification resin composition and printed wiring substrate obtained through utilizing the black solidification resin composition |
| JP2017075317A (en) * | 2016-10-27 | 2017-04-20 | クラリアント・インターナシヨナル・リミテツド | Black pigment composition for heat shielding coating, heat shielding coating using the same, use thereof for color matching and coating |
-
2019
- 2019-12-27 CN CN201911373655.2A patent/CN111381441A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281368A (en) * | 2007-04-06 | 2008-10-08 | 太阳油墨制造株式会社 | Black solder resist compound and cured product thereof |
| JP2010091876A (en) * | 2008-10-09 | 2010-04-22 | Taiyo Ink Mfg Ltd | Black solder resist composition and cured material thereof |
| CN103676476A (en) * | 2012-09-05 | 2014-03-26 | 株式会社田村制作所 | Black solidification resin composition and printed wiring substrate obtained through utilizing the black solidification resin composition |
| JP2017075317A (en) * | 2016-10-27 | 2017-04-20 | クラリアント・インターナシヨナル・リミテツド | Black pigment composition for heat shielding coating, heat shielding coating using the same, use thereof for color matching and coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112711175A (en) * | 2021-01-28 | 2021-04-27 | 杭州福斯特应用材料股份有限公司 | Black curable resin composition |
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