CN111758073A - Photosensitive resin composition, cured film, printed wiring board and method for producing same, and photosensitive resin composition production kit - Google Patents

Photosensitive resin composition, cured film, printed wiring board and method for producing same, and photosensitive resin composition production kit Download PDF

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Publication number
CN111758073A
CN111758073A CN201980014187.1A CN201980014187A CN111758073A CN 111758073 A CN111758073 A CN 111758073A CN 201980014187 A CN201980014187 A CN 201980014187A CN 111758073 A CN111758073 A CN 111758073A
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China
Prior art keywords
resin composition
photosensitive resin
meth
component
cured film
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CN201980014187.1A
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Inventor
木户雅善
小木曽哲哉
好田友洋
朝比奈勇志
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

A photosensitive resin composition comprising: (A1) a polymer having a carboxyl group and no ethylenically unsaturated group; (A2) a polymer having a carboxyl group and an ethylenically unsaturated group; (B) a compound having an ethylenically unsaturated group and having no carboxyl group; (C) a thermosetting resin; (D) a metal deactivator; (E) a photopolymerization initiator; and (F) a colorant. The cured film can be formed by irradiating a coating film of the photosensitive resin composition with active light and then thermally curing the coating film by heating.

Description

Photosensitive resin composition, cured film, printed wiring board and method for producing same, and photosensitive resin composition production kit
Technical Field
The present invention relates to: the photosensitive resin composition contains a colorant, a cured film obtained by curing the photosensitive resin composition, and a printed wiring board with a cured film, wherein the printed wiring board is provided with the cured film. Further, the present invention relates to a kit for producing the photosensitive resin composition.
Background
Since a surface protective material for a Flexible Printed Circuit (FPC) is required to have high heat resistance, a cured film obtained by curing a resin composition by photocuring or thermocuring is used. As a method for improving the heat resistance of a cured film, it is known to increase the crosslinking density of a resin composition, increase the aromatic ring content, and the like (for example, patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-008267
Patent document 2: japanese patent laid-open No. 2001 and 249450
Disclosure of Invention
Problems to be solved by the invention
In general, the FPC is mounted in a housing of the device and is not recognized from the outside in general use. Therefore, from the viewpoint of appearance, there has been no demand for a surface protective material for FPC. On the other hand, in recent years, there has been an increasing demand for visual uniformity and appearance in the interior of the device when the housing is removed for the purpose of exchange, addition, maintenance, and the like of parts. Along with this, the demand for a coloring material such as black or red has also increased for components to be mounted in the housing of the device.
A surface protective material colored in various colors can be obtained by adding a coloring agent such as a dye or a pigment to a resin composition constituting the surface protective material for FPC. However, a cured film (colored cured film) of a photosensitive resin composition to which a colorant is added may have inferior heat resistance to a case where the composition is the same except for the colorant, as compared with a case where the composition does not contain the colorant.
In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition containing a colorant and having a cured film with excellent heat resistance.
Means for solving the problems
The resin composition of the present invention contains: (A) a polymer having a carboxyl group, (B) a compound having at least 1 ethylenically unsaturated group in the molecule and having no carboxyl group, (C) a thermosetting resin, (D) a metal deactivator, (E) a photopolymerization initiator, and (F) a colorant. (A) The components comprise: (A1) a polymer having a carboxyl group and no ethylenically unsaturated group; and (A2) a polymer having a carboxyl group and an ethylenically unsaturated group.
(A1) The component (A2) preferably has an acid value of 5 to 200mgKOH/g and a weight-average molecular weight of 1000 to 1000000. (A2) Component (b) is preferably a polymer containing at least 1 carboxyl group and 2 or more (meth) acryloyl groups in 1 molecule. Preferable examples of the component (a2) include: an acid-modified epoxy (meth) acrylate obtained by adding a saturated or unsaturated polycarboxylic anhydride to an ester obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid.
Specific examples of the ethylenically unsaturated group in the component (A2) and the component (B) include a vinyl group and a (meth) acryloyl group. (A2) Both of the component (A) and the component (B) are preferably a polyfunctional (meth) acrylic compound having 2 or more (meth) acryloyl groups in 1 molecule.
As the component (B), a compound containing 3 or more (meth) acryloyl groups in 1 molecule can also be used. The component (B) preferably contains a polyfunctional (meth) acrylate having a functional group equivalent of a (meth) acryloyl group of 80 to 300 from the viewpoint of increasing the crosslinking density. As the component (B), a polyfunctional (meth) acrylic compound containing 3 or more (meth) acryloyl groups in 1 molecule and having a functional group equivalent of the (meth) acryloyl group of 80 to 300 can also be used. A polyfunctional (meth) acrylate having a functional group equivalent of (meth) acryloyl group of 80 to 300 and a polyfunctional (meth) acrylic oligomer may be used in combination. By using a polyfunctional (meth) acrylic oligomer in combination, flexibility of the cured film tends to be improved.
The component (C) is preferably a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule, and particularly preferably a polyfunctional epoxy resin having a weight average molecular weight of 1500 or less.
As the component (D), for example, a benzamide derivative having a phenolic hydroxyl group or a hydrazide derivative having a phenolic hydroxyl group can be used.
As the component (E), a photo radical polymerization initiator having an absorption band at a wavelength of 405nm is preferable. The photo radical polymerization initiator preferably has an absorption coefficient at a wavelength of 405nm of 20 [% ]-1·cm-1]The above. Specific examples of the component (E) include oxime esters.
The content of (a) (the total of the contents of (a1) and (a 2)) in the photosensitive resin composition is preferably 30 to 80 parts by weight relative to 100 parts by weight of the total of the contents of (a), (B) and (C). (B) The content of (C) is preferably 5 to 30 parts by weight, and the content of (C) is preferably 10 to 40 parts by weight.
The photosensitive resin composition can also be provided in the form of a kit containing at least the 1 st agent and the 2 nd agent independently. That is, the photosensitive resin composition preparation kit independently contains the 1 st agent and the 2 nd agent. The photosensitive resin composition can be prepared by mixing the 1 st agent and the 2 nd agent.
In a preferred embodiment, the kit comprises component (A) in the 1 st dose and component (D) in the 2 nd dose. When the storage is performed without mixing the component (a) and the component (D), the stability of the solution tends to be improved. The 1 st part of the kit may contain the component (B) in addition to the components (A1) and (A2), and the 2 nd part of the kit may contain the component (E) in addition to the component (D). The 2 nd agent of the kit may also comprise the component (C).
The photosensitive resin composition is photo-cured and thermally cured to obtain a cured film. The printed circuit board with the cured film can be formed, for example, by the following method: the photosensitive resin composition is applied to the surface of a printed wiring board to form a coating film, at least a part of the surface of the coating film is irradiated with active light to be photo-cured, and if necessary, the coating film is developed with alkali or the like, and then the photo-cured coating film is heated to be thermally cured. The printed wiring board may be a flexible printed wiring board using a flexible film base material such as a polyimide film.
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive resin composition of the present invention can realize high heat resistance even when a colored cured film is formed on a metal wiring of a printed wiring board.
Detailed Description
The photosensitive resin composition of the present invention contains: (A) a carboxyl group-containing polymer, (B) a photocurable compound having an ethylenically unsaturated group, (C) a thermosetting resin, (D) a metal deactivator, (E) a photopolymerization initiator, and (F) a colorant. (A) The components comprise: (A1) a polymer having a carboxyl group and no ethylenically unsaturated group; and (A2) a compound having a carboxyl group and an ethylenically unsaturated group.
(A) Since the component (C) has a carboxyl group, the photosensitive resin composition is alkali-soluble. In the photosensitive resin composition, the component (E) is activated by exposure to light (irradiation with active light), and the photo radical polymerization reaction of the component (a2) and the component (B) proceeds. By photo-curing, the resin composition becomes insoluble in alkali. When the resin composition is heated, the component (C) is thermally cured. When thermally cured, the carboxyl groups of the components (A1) and (A2) react with the component (C) to form a crosslinked structure. (A2) The component contributes to both the formation of a photo-crosslinked network based on photocuring and the formation of a thermal-crosslinked network based on thermal curing, and therefore, a cured film having high film strength and heat resistance can be formed. (A1) The component (a) is not photocurable and contributes only to the formation of a thermally crosslinked network. Therefore, the cured film can be made flexible.
The photosensitive resin composition containing the component (D) can suppress the inhibition of a curing reaction caused by a metal (ion) at the interface with a metal layer such as a copper foil, and the deterioration of a cured film. The photosensitive resin composition can be provided with a cured film colored in a desired color such as black by containing the component (F).
Preferred embodiments of the respective components constituting the photosensitive resin composition will be described below in order. Unless otherwise specified, the following components may be used alone or in combination of two or more. In the present specification, "(meth) acrylic" means acrylic acid or methacrylic acid, and "(meth) acryloyl" means acryloyl or methacryloyl.
< A carboxyl group-containing Polymer >
(A) The component (A) is a polymer having at least 1 carboxyl group in the molecule, and is a main component for forming a coating film based on the resin composition. (A) The component (A) is soluble in an organic solvent. Examples of the organic solvent capable of dissolving the component (A) include sulfoxides, formamides, acetamides, pyrrolidones, phosphoramides, lactones, ethers, and acetates. (A) The component (b) is preferably soluble in any of these organic solvents at a concentration of 5% by weight or more.
(A) The weight average molecular weight of the component (A) in terms of polyethylene glycol is preferably 1000 to 1000000, more preferably 2000 to 200000, still more preferably 3000 to 100000, and particularly preferably 4000 to 50000. If the weight average molecular weight of the carboxyl-group-containing compound is within the above range, a cured film excellent in heat resistance and flexibility is easily obtained.
Since the photosensitive resin composition has a carboxyl group-containing polymer as the component (a), the photosensitive resin composition before curing exhibits alkali solubility. The carboxyl group of the component (a) contained in the photosensitive resin composition may be a carboxylic anhydride obtained by dehydrating 2 carboxyl groups.
(A) The acid value of the component (A) is preferably 5 to 200mgKOH/g, more preferably 10 to 150mgKOH/g, and still more preferably 15 to 100 mgKOH/g. When the acid value of the component (a) is in the above range, the photosensitive resin composition before curing exhibits appropriate alkali solubility. In addition, by setting the acid value within the above range, the heat resistance, insulation reliability, and chemical resistance of the cured film can be improved, and flexibility can be imparted.
As described above, the (a) component contains: (A1) a polymer having no ethylenically unsaturated group, and (A2) a polymer having an ethylenically unsaturated group. (A1) The ingredient facilitates the formation of a thermally crosslinked network and does not facilitate the formation of a photocrosslinked network. (A2) The ingredient facilitates both the formation of a thermally crosslinked network and the formation of a photocrosslinked network.
< A1A carboxyl group-containing polymer having no ethylenically unsaturated group >
(A1) The component (A) is a polymer containing a carboxyl group and no ethylenically unsaturated group. Specific examples of the component (a1) include carboxyl group-containing (meth) acrylic polymers, carboxyl group-containing vinyl polymers, acid-modified polyurethanes, acid-modified polyesters, acid-modified polycarbonates, acid-modified polyamides, acid-modified polyimides, acid-modified polyurethane amides, acid-modified polyurethane imides, and the like. From the viewpoint of flexibility and chemical resistance of the cured film, a carboxyl group-containing (meth) acrylic copolymer, an acid-modified polyurethane, an acid-modified polyamide, and an acid-modified polyimide are preferable.
(A1) The component (b) can be obtained by various known methods. The polymerization may be either solution polymerization or solvent-free polymerization, but solution polymerization is preferable for controlling the reaction. The organic solvent for solution polymerization is not particularly limited as long as it can dissolve both the monomer component and the polymer after polymerization. The amount of the solvent in the solution polymerization may be adjusted so that the solution concentration is 5 to 90% by weight, preferably 20 to 70% by weight.
The carboxyl group-containing (meth) acrylic polymer is a copolymer containing, as monomer components, (meth) acrylate and 1 molecule of a compound having a carboxyl group and a polymerizable double bond. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, isocrotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, ω -carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, (meth) acrylic acid dimer, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, atropic acid, cinnamic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, midic acid, dihomo- γ -linolenic acid, eicosatrienoic acid, octadecatetraenoic acid, arachidonic acid, eicosatetraenoic acid, Adrenic acid, octadecenoic acid, eicosapentaenoic acid, docosapentaenoic acid, herring acid, tetracosapentaenoic acid, docosahexaenoic acid, tetracosahexaenoic acid, 2,2, 2-tri (meth) acryloyloxymethyl succinic acid, 2-tri (meth) acryloyloxymethyl ethyl phthalic acid, etc. As the (meth) acrylate, alkyl (meth) acrylates are preferable.
The carboxyl group-containing (meth) acrylic polymer may contain, as a copolymerization component, a (meth) acrylamide such as diacetone (meth) acrylamide, an ester of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether, styrene, vinyl toluene, and the like, in addition to the carboxyl group-containing monomer and the (meth) acrylic acid ester. The carboxyl group-containing (meth) acrylic polymer is obtained by, for example, radical polymerization of the above-mentioned monomer components. The radical polymerization may be thermal polymerization or photopolymerization. Polymerization initiators can also be used in the free-radical polymerization. The carboxyl group-containing (meth) acrylic polymer is preferably obtained by solution polymerization using an azo compound, an organic peroxide, a persulfate, hydrogen peroxide, or the like as a thermal polymerization initiator.
The acid-modified polyurethane is obtained by, for example, reacting a diol compound having 2 hydroxyl groups and 1 carboxyl group with a diisocyanate compound.
The acid-modified polyester is obtained by, for example, reacting a diol compound having 2 hydroxyl groups and 1 carboxyl group with a dicarboxylic acid.
The acid-modified polyamide is a compound having an amic acid structure, and is obtained, for example, by reacting a diamino compound with a tetracarboxylic dianhydride.
The acid-modified polyimide is obtained, for example, by reacting a diisocyanate compound with a tetracarboxylic dianhydride. By adding a tetracarboxylic dianhydride in an excess amount equivalent to the diisocyanate compound, an imide compound having a carboxylic anhydride group at the terminal can be obtained. An imide compound having a carboxyl group at the terminal can be obtained by reacting an imide compound having a carboxylic anhydride group at the terminal with water and/or a primary alcohol such as methanol, ethanol, propanol, or butanol.
Examples of the diol compound having 2 hydroxyl groups and 1 carboxyl group include aliphatic diols such as 2, 2-bis (hydroxymethyl) propionic acid, 2-bis (2-hydroxyethyl) propionic acid, 2-bis (3-hydroxypropyl) propionic acid, 2, 3-dihydroxy-2-methylpropionic acid, 2-bis (hydroxymethyl) butyric acid, 2-bis (2-hydroxyethyl) butyric acid, 2-bis (3-hydroxypropyl) butyric acid, 2, 3-dihydroxybutyric acid, 2, 4-dihydroxy-3, 3-dimethylbutyric acid, and 2, 3-dihydroxyhexadecanoic acid; aromatic diols such as 2, 3-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, and 3, 5-dihydroxybenzoic acid. In particular, when an aliphatic diol is used, the photosensitive resin composition tends to have excellent photosensitivity.
The diisocyanate compound may be an alicyclic diisocyanate compound or an aliphatic diisocyanate compound. The diisocyanate compound may be a reaction product of a compound having two or more functional groups capable of reacting with an isocyanate group of the diisocyanate compound, and may be, for example, a urethane compound having an isocyanate group at an end.
The tetracarboxylic dianhydride may be either an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride, and is preferably an aromatic tetracarboxylic dianhydride in which a carboxylic anhydride group is directly bonded to an aromatic ring. Among them, aromatic tetracarboxylic dianhydrides are preferred, and carboxylic anhydride groups are preferred as being directly bonded to aromatic rings. The diamino compound may be both aromatic diamine and aliphatic diamine, and preferably aromatic diamine.
< A2 ] Polymer having carboxyl group and ethylenically unsaturated group
(A2) The component (A) is a polymer having an ethylenically unsaturated group in addition to a carboxyl group. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group. (A2) Since the component (C) reacts with the component (C) during thermal curing and the component (B) during photo-curing, the crosslinking density of the cured film tends to be increased and the heat resistance and chemical resistance tend to be improved.
Examples of the component (a2) include acid-modified epoxy (meth) acrylates obtained by adding a saturated or unsaturated polycarboxylic anhydride to an ester obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid; urethane (meth) acrylates as polymers of diol compounds having an ethylenically unsaturated group and/or a carboxyl group and diisocyanate compounds; and (meth) acrylated (meth) acrylates obtained by reacting a part of the carboxyl groups in the side chain of a copolymer of (meth) acrylic acid having a carboxyl group and a polymerizable double bond and (meth) acrylate with the epoxy groups of a compound having a (meth) acrylic group and an epoxy group, such as glycidyl (meth) acrylate.
Examples of the saturated or unsaturated polybasic acid anhydride used for the synthesis of the epoxy (meth) acrylate include anhydrides of phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, trimellitic acid, and the like. Examples of the skeleton structure of the acid-modified epoxy (meth) acrylate (skeleton structure of the epoxy resin) include bisphenol a type, bisphenol E type, bisphenol F type, biphenyl type, cresol novolac type, phenol novolac type, and the like. As the component (a2), an acid-modified epoxy (meth) acrylate obtained by introducing a structure having high flexibility such as a polyoxyalkylene group or a polyurethane chain into the skeleton of an epoxy resin can be used. By using a polymer having a soft skeleton structure such as a polyurethane chain as the component (a2), the flexibility of the cured film tends to be improved.
Examples of commercially available epoxy (meth) acrylates having a carboxyl group include KAYARAD ZFR series, ZAR series, ZCR series, CCR series, PCR series, and UXE series, which are manufactured by japan chemical corporation. Commercially available urethane (meth) acrylates having a carboxyl group include UX series manufactured by Nippon Kagaku K.K.K.K.K.K.K.K.K.. Commercially available (meth) acrylated (meth) acrylates include Cyclomer ACA series manufactured by Daicel-Cytec.
The content of the component (A) (the total of the contents of (A1) and (A2)) is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, and still more preferably 30 to 60 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. The content of the component (A) is preferably 30 to 80 parts by weight, more preferably 40 to 75 parts by weight, and still more preferably 50 to 70 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B), and the component (C). When the amount of the component (A) is adjusted within the above range, the heat resistance and chemical resistance of the cured film tend to be improved.
The content of the component (A1) is preferably 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, and still more preferably 20 to 40 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B), and the component (C). The content of the component (A2) is preferably 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, and still more preferably 20 to 40 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B), and the component (C). (A1) The ratio (A2)/(A1) of the content of the component (A2) to the content of the component (A2) is preferably 0.2 to 5, more preferably 0.5 to 2, and still more preferably 0.7 to 1.5.
[ Photocurable Compound (B) ]
(B) The component (A) is a photocurable compound having at least 1 ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group. (B) The component (A) forms a photocrosslinked network together with the above-mentioned component (A2). Component (a2) contains a carboxyl group and contributes to the formation of a thermally crosslinked network together with component (C), whereas component (B) does not contain a carboxyl group and contributes only to the formation of a photocrosslinked network.
Specific examples of the compound having a (meth) acryloyl group include stearyl (meth) acrylate, lauryl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxy glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, β - (meth) acryloyloxyethylhydrogen phthalate, β - (meth) acryloyloxyethylhydrogen succinate, 3-chloro-2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxyethyl hydrogen phthalate, and the like, Monofunctional (meth) acrylic compounds such as 1- (meth) acryloyloxypropyl-2-phthalate and polyoxyethylene alkyl ether (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1- (meth) acryloyloxy-3- (meth) acryloyloxypropane, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2, 4-diethyl-1, 5-pentanediol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 3-methyl-1, 5-pentanediol di (meth) acrylate, 2, 4-diethyl-1, 5-pentanediol di (meth) acrylate, 1, 4-cyclohexanedimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 4' -isopropylidenediphenol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxy-diethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxy-polyethoxy) phenyl ] propane, Polyfunctional (meth) acrylic compounds such as 2, 2-hydrogenated bis [4- ((meth) acryloyloxy-polyethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxy-polypropoxy) phenyl ] propane, bisphenol F EO-modified (n ═ 2 to 50) di (meth) acrylate, bisphenol a EO-modified (n ═ 2 to 50) di (meth) acrylate, and bisphenol S EO-modified (n ═ 2 to 50) di (meth) acrylate.
The polyfunctional (meth) acrylic compound may have 3 or more (meth) acryloyl groups in 1 molecule. Examples of the 3-or higher-functional (meth) acrylic compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, isocyanuric acid tri (ethane (meth) acrylate), 1,3, 5-tri (meth) acryloyl hexahydro-s-triazine, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, and the like.
Specific examples of the compound having a vinyl group include diallylamine, diallyldimethylsilane, diallyldisulfide, diallylether, diallylcyanurate, diallyldiphthalate, diallylterephthalate, 1, 3-diallyloxy-2-propanol, diallylsulfonyldiallylmaleite, triallylisocyanurate, triallyl 1,3, 5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, and the like.
(B) The component (b) may be a polymer (oligomer) such as a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, or an acrylic (meth) acrylate resin.
From the viewpoint of heat resistance of the cured film, it is preferable to use a polyfunctional (meth) acrylic compound containing 2 or more (meth) acryloyl groups in 1 molecule as the component (B). By using a polyfunctional (meth) acrylic compound, a photocrosslinked network based on the (B) component is formed together with the (B) component. From the viewpoint of increasing the crosslinking density, a polyfunctional (meth) acrylic compound containing 3 or more (meth) acryloyl groups in 1 molecule may also be used as the component (B).
From the viewpoint of increasing the crosslinking density of the cured film, the molecular weight of the polyfunctional (meth) acrylic compound containing 3 or more (meth) acryloyl groups is preferably 1000 or less, more preferably 800 or less, and even more preferably 700 or less.
From the viewpoint of increasing the crosslinking density, it is preferable to use, as the component (B), a polyfunctional (meth) acrylic compound having a functional group equivalent of (meth) acryloyl group (mass (g) of the compound containing 1 equivalent of (meth) acryloyl group) of 300 or less. The polyfunctional (meth) acrylic compound usually has a functional group equivalent of 80 or more. From the viewpoint of increasing the crosslinking density of the cured film to improve the heat resistance, the functional group equivalent of the polyfunctional (meth) acrylic compound is more preferably 250 or less, and still more preferably 200 or less. The polyfunctional (meth) acrylic compound may have a functional group equivalent of 180 or less or 150 or less.
As described above, it is preferable to use a polyfunctional (meth) acrylate having 3 or more functional groups with a functional group equivalent of a (meth) acryloyl group of 300 or less as the component (B). In a cured film having a photocrosslinked network formed from a 3-or more-functional polyfunctional (meth) acrylate, since a plurality of polymer chains of the component (a2) are present in close proximity (the crosslinking distance is short), a structure having a high crosslinking density and strength is easily formed, and the heat resistance tends to be improved.
On the other hand, when the short-distance crosslinking structure density of the polyfunctional (meth) acrylate having a small functional group equivalent based on the (meth) acryloyl group (i.e., having a high functional group density) becomes too high, the flexibility of the cured film may be reduced. From the viewpoint of improving the crosslinking density to improve the heat resistance and improving the flexibility of the cured film, a polyfunctional (meth) acrylic oligomer may be used as the component (B) in addition to the polyfunctional (meth) acrylic compound having a small functional group equivalent. In particular, by using a 3-or more-functional (meth) acrylic compound and a polyfunctional (meth) acrylic oligomer as the component (B), a short-distance crosslinked structure and a long-distance crosslinked structure coexist, and thus a cured film having improved heat resistance and flexibility can be easily formed.
Examples of the polyfunctional (meth) acrylic oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and acrylic (meth) acrylate. Urethane (meth) acrylate is preferable in terms of ease of forming a cured film having excellent flexibility. The polyfunctional (meth) acrylic oligomer is preferably a 2-functional (meth) acrylic compound.
The molecular weight of the polyfunctional (meth) acrylic oligomer is preferably about 250 to 20000, more preferably 300 to 15000, and still more preferably 350 to 10000, from the viewpoint of satisfying both heat resistance and flexibility of the cured film. The molecular weight of the polyfunctional (meth) acrylic oligomer may be 400 or more, or 5000 or less, 3000 or less, 2000 or less, 1500 or less, or 1000 or less.
The (meth) acryloyl group of the polyfunctional (meth) acrylic oligomer may be either an acryl group or a methacryl group. As described above, oligomers having acryloyl groups at both ends are often used in order to improve photocurability, but methacrylic oligomers such as urethane dimethacrylate having methacryloyl groups at both ends may be used in order to improve flexibility of a cured film by appropriately adjusting photocrosslinking properties. When a methacrylic compound is used as the component (B), the reactivity of photo radical polymerization is lower than that in the case of using an acrylic compound, and therefore, an unreacted (uncured) methacrylic compound is likely to remain after photocuring. The unreacted oligomer functions as a plasticizer in the cured film, and therefore, it is considered to contribute to improvement in flexibility of the cured film.
The content of the component (B) is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, still more preferably 5 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. The content of the component (B) is preferably 5 to 30 parts by weight, more preferably 8 to 25 parts by weight, and still more preferably 10 to 20 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). By adjusting the amount of the component (B) within the above range, it becomes easy to achieve both flexibility and heat resistance of the cured film.
(B) When the component (A) contains a polyfunctional (meth) acrylic compound having 3 or more functions and a polyfunctional (meth) acrylic oligomer having 2 or more functions, the content of the polyfunctional (meth) acrylic compound having 3 or more functions is preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight, and still more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B), and the component (C). The content of the polyfunctional (meth) acrylic oligomer is preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight, and still more preferably 5 to 15 parts by weight.
< C thermosetting resin >
The thermosetting resin is a compound having at least 1 thermosetting functional group in a molecule. As the thermosetting resin, epoxy resin, oxetane resin, isocyanate resin, blocked isocyanate resin, cyanate resin are preferable. Among them, epoxy resins are preferable from the viewpoint of being capable of reacting with the carboxyl group of the component (a) to form a thermally crosslinked network. From the viewpoint of imparting heat resistance to the cured film and also imparting adhesion to a conductor such as a metal foil or a circuit board, a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
Examples of the polyfunctional epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, biphenyl type epoxy resin, phenoxy type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, amine type epoxy resin, and the like. The epoxy resin may be a modified epoxy resin based on urethane, rubber, chelate, dimer acid, or the like. As the component (C), a commercially available epoxy resin can be used as it is.
The epoxy equivalent (mass (g) of the compound containing 1 equivalent of epoxy group) of the epoxy resin is preferably 2000 or less, more preferably 1500 or less, from the viewpoint of heat resistance and chemical resistance of the cured film. The epoxy resin preferably has a weight average molecular weight of about 150 to 2000, more preferably about 200 to 1500.
The content of the component (C) is preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. The content of the component (C) is preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, and still more preferably 20 to 30 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B), and the component (C). By adjusting the amount of component (C) within the above range, a cured film having excellent heat resistance and chemical resistance and flexibility can be easily obtained.
< D Metal deactivator >
The metal deactivator is deactivated by forming a complex with a metal, and thus has an action of suppressing the curing reaction caused by the metal (ion) and the deterioration of the cured film. Examples of the deactivator capable of forming a complex with copper include polybasic acids such as oxalic acid and malonic acid; amino acids such as glycine and proline; an amide compound; hydrazide compounds, and the like.
The metal deactivator is preferably a compound which has little residue on the metal surface in the region from which the film has been removed by development. When a metal deactivator having a strong binding force with a metal is used, the deactivator on the metal surface cannot be sufficiently removed even by rinsing after development, and the residue of the deactivator may be recognized as a defect. In particular, when a colored cured film (typically, a black cured film) formed by curing a photosensitive composition containing a colorant is patterned, a metal adhering to a surface exposed to the colored cured film is more easily recognized than a non-colored film. Therefore, the metal deactivator is preferably a substance which has a suitable binding property to a metal such as copper and can be easily removed from the metal surface by development and/or washing after development.
In view of having a suitable binding property to copper and excellent deactivation and removal from the metal surface, a benzamide derivative having a phenolic hydroxyl group such as N- (2H-1,2, 4-triazol-5-yl) salicylamide (commercially available as "adekasab CDA-1" manufactured by ADEKA) is preferable as the metal deactivator; hydrazide derivatives having a phenolic hydroxyl group such as N ' 1, N ' 12-bis (2-hydroxybenzoyl) dodecanedihydrazide ("Adekastab CDA-1" manufactured by ADEKA) and N ' -bis {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl } hydrazine ("Adekastab CDA-10" manufactured by ADEKA) are commercially available.
The content of the component (D) is preferably 0.1 to 1.0 part by weight, more preferably 0.2 to 0.5 part by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. By adjusting the amount of the component (D) within the above range, the heat resistance of the cured film can be improved by suppressing the inhibition of polymerization, and the deterioration of the performance and appearance due to the residue can be suppressed. When the amount of the component (D) is within the above range, deterioration of the cured film in the vicinity of the interface with the metal tends to be suppressed.
< E) photopolymerization initiator
The photopolymerization initiator as the component (E) is a compound of: the component (a) is activated by absorbing light energy such as UV (ultraviolet light), and initiates/accelerates formation of a photocrosslinked network (photoradical polymerization initiator) by photoradical polymerization reaction of the ethylenically unsaturated groups of the component (a2) and the component (B).
Examples of the photo radical polymerization initiator include self-cleavage type photo radical polymerization initiators such as benzoin-based compounds, acetophenones, aminoketones, oxime esters, acylphosphine oxide-based compounds, and azo-based compounds; and hydrogen abstraction type photo-radical polymerization initiators such as benzophenones, benzoin ethers, benzil ketals, dibenzosuberone, anthraquinones, xanthones, 9-thioxanthones, halogenated acetophenones, dialkoxyphenones, hydroxyacetophenones, halogenated bisimidazoles, halotriazines, etc.
As the photo radical polymerization initiator, a photo radical polymerization initiator having an absorption band at a wavelength of 405nm is preferable. By using a photo radical polymerization initiator having an absorption band at a wavelength of 405nm, the heat resistance of the cured film tends to be improved. The photo radical polymerization initiator preferably has an absorbance of 0.02 or more at a wavelength of 405nm of a 0.001 wt% methanol solution measured by a visible-ultraviolet spectrophotometer using a quartz cuvette having an optical path length of 1 cm. In other words, it is preferable to use an absorption coefficient of 20 [% ] at a wavelength of 405nm-1·cm-1]The above photo radical polymerization initiator.
Examples of the photo radical polymerization initiator having an absorption band at 405nm include acylphosphine oxide compounds, acetophenones, aminoketones, and oxime esters. Among them, oxime esters are preferable in view of high photosensitivity. Examples of commercially available oxime esters having an absorption band at a wavelength of 405nm include "ADEKA ARKLS NCI-831", "ADEKAARKLS N-1717" and "ADEKA ARKLS N-1919" manufactured by ADEKA, and "Irgacure OXE 03" manufactured by BASF.
The content of the component (E) is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and still more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the solid components of the component (A2) and the component (B). By setting the compounding ratio as described above, the photosensitivity of the photosensitive resin composition is improved, the photocuring reaction efficiency can be improved, and overexposure can be prevented.
< (F) colorant
The colorant is added to make the cured film a desired color. The colorant can be dye or pigment. Examples of the colorant include a blue colorant, a red colorant, a yellow colorant, an orange colorant, and a violet colorant. By combining a plurality of colorants, cured films of various colors can be formed. Specific examples of the colorant are shown below as a dye index number.
Examples of the Blue colorant include c.i. pigment Blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60; solvent Blue35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 as dye system. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound may also be used as the blue colorant. From the viewpoint of coloring power, a copper phthalocyanine-based colorant is particularly preferable.
Examples of the Red colorant include c.i. pigment Red 122, 149, 166, 177, 179, 242, 224, 254, 264, and 272.
Examples of the Yellow colorant include c.i. pigment Yellow 83, 110, 128, 138, 139, 150, 151, 154, 155, 180, and 181.
Examples of Orange colorants include c.i. pigment Orange 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.
Examples of the Violet colorant include c.i. pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; solvent Violet 13, 36.
Combinations of the above colorants may also be used as black colorants. Specific examples of combinations of colorants for making the cured film black are shown below. The following ratios represent weight ratios.
The orange colorant is combined at a ratio of 1.5 to 3.0 relative to 1.0 of the blue colorant.
The red colorant is combined at a ratio of 1.2 to 3.0 with respect to 1.0 of the blue colorant.
The violet colorant is combined at a ratio of 1.2 to 3.0 relative to 1.0 of the blue colorant.
The ratio of yellow colorant 1.5-4 to orange colorant 1.0-2.5 is used to the blue colorant 1.0.
The ratio of the red colorant 1.0-2.0 to the blue colorant 1.0 and the yellow colorant 1.5-3.0 are combined.
The ratio of the yellow colorant 1.0 to 3.0 to the violet colorant 1.0 to 2.0 is used in combination with respect to the blue colorant 1.0.
The orange colorant is 0.5 to 2.0 and the violet colorant is 0.5 to 2.0 relative to 1.0 of the blue colorant.
Among the above, a combination of a blue colorant, an orange colorant and a violet colorant is preferable in terms of excellent blackness and easy adjustment of the colorant amount.
(F) The content of the component (b) may be appropriately set depending on the kind of the colorant and the color of the cured film. For example, in order to obtain a black cured film, the content of the component (F) is preferably 3 parts by weight or more, and more preferably 4 parts by weight or more, based on 100 parts by weight of the total solid content of the photosensitive resin composition. From the viewpoint of coloring properties, there is no particular problem in that the amount of the colorant is large, but as the amount of the colorant increases, photocurability tends to decrease, and photocuring at the interface with the metal layer (the interface at the bottom when viewed from the light irradiation surface) may become insufficient. In addition, when the amount of the colorant is large, the thixotropic index may be increased, clogging may occur during ink filtration, the printability may be deteriorated, and the resolution may be lowered. Therefore, the content of the component (F) is preferably 10 parts by weight or less, more preferably 7 parts by weight or less, relative to 100 parts by weight of the total solid content of the photosensitive resin composition.
< other ingredients >
The photosensitive resin composition may contain, in addition to the components (a) to (F), various additives such as a filler, an adhesion aid, an antifoaming agent, a leveling agent, a polymerization inhibitor, and a flame retardant, if necessary. Examples of the filler include inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate, and organic polymer fillers. Examples of the defoaming agent and the leveling agent include a silicone compound and an acrylic compound. Examples of the adhesion auxiliary agent (also referred to as adhesion imparting agent) include a silane coupling agent, a triazole-based compound, a tetrazole-based compound, and a triazine-based compound. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether.
As the flame retardant, a phosphate-based compound, a halogen-containing compound, a metal hydroxide, an organophosphorus-based compound, an organosilicon-based compound, or the like can be used. From the viewpoint of environmental pollution prevention, non-halogen flame retardants such as metal hydroxides and phosphorus compounds are preferred.
< preparation of photosensitive resin composition >
The photosensitive resin composition can be obtained by mixing the above components and, if necessary, an appropriate solvent. The above-mentioned components may be subjected to operations such as pulverization, dispersion, and defoaming before and/or after mixing, as required. The pulverization/dispersion may be carried out using a kneading apparatus such as a bead mill, a ball mill, or a three-roll mill.
The photosensitive resin composition may be provided in the form of a kit containing a part of the components and other components independently. For example, the photosensitive resin composition preparation kit independently contains the 1 st agent and the 2 nd agent. When a plurality of components to be reacted are mixed in a solution state, the storage stability of the solution may be lowered, but by storing the mixture without mixing the components, the stability of the solution can be improved, and the lead time such as transportation and storage can be flexibly coped with.
In the above-mentioned photosensitive resin composition, when the carboxyl group-containing polymer (a) and the metal deactivator (D) coexist in the solution, the viscosity may increase with time. Therefore, from the viewpoint of improving storage stability, it is possible to provide a kit for producing a photosensitive resin composition containing the component (a) in the 1 st agent and the component (D) in the 2 nd agent. By storing the component (A) and the component (D) in the form of a kit containing the 1 st and 2 nd agents independently without mixing them, the increase in viscosity can be suppressed.
The 1 st dose of the kit may contain the component (B) in addition to the components (A1) and (A2), and the 2 nd dose of the kit may contain the component (E) in addition to the component (D). By storing the component (a2) and the component (B) having photopolymerization (photosensitivity) without mixing them with the photopolymerization initiator (E), photocuring in a storage environment can be suppressed. The 2 nd agent of the kit may also comprise the component (C). By storing the component (a) without mixing the carboxyl group-containing polymer (a) with the epoxy resin (C), a reaction between the carboxyl group of the component (a) and the functional group of the component (C), such as an epoxy group, can be prevented in the storage environment.
When the photosensitive resin composition preparation kit is of a two-pack type containing the 1 st agent and the 2 nd agent, the component (F) may be contained in either the 1 st agent or the 2 nd agent, or both. The photosensitive resin composition can be prepared by mixing the composition of the 1 st agent and the composition of the 2 nd agent constituting the kit. The photosensitive resin composition preparation kit is not limited to the two-component type containing the 1 st agent and the 2 nd agent, and may be a three-component or higher mixed type.
< formation of cured film >
The photosensitive resin composition is applied onto a substrate, and if necessary, the solvent is removed by heating, and then photocured and thermally cured to form a cured film. Since the photosensitive resin composition contains a colorant, a colored cured film colored black or the like is obtained. By using the photosensitive composition, a cured film having excellent heat resistance can be formed on a metal such as a copper foil.
In general, when a resin composition containing a coloring agent such as black is photocured, the cured film is insufficiently cured in the vicinity of the interface opposite to the light irradiation surface, and the heat resistance may be poor. In particular, when a cured film is formed on a metal, heat resistance is likely to be lowered. One cause of the decrease in heat resistance when a cured film is formed on a metal is inhibition of polymerization in the vicinity of the interface between the metal and the cured film, and decomposition of the resin. In particular, in the presence of metal ions, decomposition of the resin is promoted, and therefore, it is considered that the adhesion at the interface with the metal is reduced and the heat resistance of the cured film is likely to be reduced.
As described above, it is considered that the photosensitive resin composition contains (D) a metal deactivator to suppress decomposition and polymerization of the resin caused by the metal, and to improve the adhesion at the interface between the metal and the cured film, thereby improving the heat resistance. Further, since the photosensitive resin composition contains the component (a2) contributing to both the formation of the photo-crosslinked network and the formation of the thermal-crosslinked network, it is considered that the improvement of the crosslinkability by thermal crosslinking contributes to the improvement of the heat resistance even when the photo-curing in the vicinity of the metal interface is insufficient.
When a photopolymerization initiator having an absorption band at a wavelength of 405nm is used as the component (E), the heat resistance of the cured film tends to be further improved. By using a photopolymerization initiator having an absorption band at a long wavelength, photocuring of the bottom portion (the vicinity of the interface with the metal) is easily performed even when the resin composition has a colorant, which contributes to improvement of heat resistance.
When a coating film of the photosensitive resin composition is irradiated with active light such as ultraviolet light or short-wavelength visible light, the photopolymerization initiator in the vicinity of the irradiated surface absorbs light to activate, and light that is not absorbed in the vicinity of the irradiated surface reaches the bottom (the vicinity of the interface with the metal). Therefore, in general, the irradiation surface side is more likely to advance photocuring than the bottom portion. In particular, when the photosensitive resin composition contains a colorant, the colorant absorbs active light in addition to the photopolymerization initiator, and therefore the amount of active light reaching the bottom portion is small, and the photocuring of the bottom portion tends to be insufficient compared with the light irradiation surface.
Since light having a short wavelength is relatively high energy, in photocuring by irradiation with active light, the short wavelength light is preferentially used near the light irradiation surface, and the long wavelength light that is not absorbed near the light irradiation surface easily reaches the bottom. By using a photopolymerization initiator having an absorption band at a long wavelength (405nm) as the component (E), photocuring by a long-wavelength light reaching the bottom is facilitated. Therefore, it is considered that even when the composition contains a colorant, the photo-curing reaction at the bottom is maintained, and the heat resistance of the cured film is improved.
That is, by including the metal deactivator as the component (D), the curing inhibition of the bottom portion (the vicinity of the interface with the metal) and the decomposition of the resin can be suppressed, and by using the photopolymerization initiator having an absorption band at a long wavelength, the photocuring reactivity of the bottom portion is improved. Further, even when the composition contains a coloring agent such as black, the heat curing proceeds uniformly so that there is little difference in the thickness direction of the film, and therefore, the insufficient curing at the bottom can be compensated. Therefore, it is considered that a cured film having excellent adhesion at the interface with the metal, high crosslinking density even in the vicinity of the interface with the metal, and excellent heat resistance is formed.
The formation of the cured film using the photosensitive resin composition can be carried out by various known methods. The photosensitive resin composition (solution) may be applied to the substrate by screen printing, curtain coating, reverse roll, spray coating, spin coating using a spinner, or the like. The thickness of the coating film may be adjusted so that the thickness after drying is about 5 to 100 μm, preferably about 10 to 50 μm. When drying is performed by heating, the drying temperature is preferably 120 ℃ or less, and more preferably 40 to 100 ℃ from the viewpoint of suppressing the thermosetting reaction.
The dried coating film is exposed to light to be cured. In the exposure, a photomask is placed on the coating film, and a portion of the coating film in the plane is selectively exposed and then developed, whereby a relief pattern can be formed. During exposure, active light such as ultraviolet light and visible light is irradiated. When a photopolymerization initiator having an absorption band at a long wavelength is used as the component (E), it is preferable that exposure is performed by a light source containing light having a short wavelength (for example, 400 to 450nm) of visible light. When the exposure is performed using an LED, an LED having an emission peak wavelength longer than 385nm is preferably used.
As the developer, an aqueous alkali solution is generally used, and an aqueous organic alkali solution and an aqueous inorganic alkali solution can be used without particular limitation. The developer may also contain an organic solvent having miscibility with water, such as methanol, ethanol, N-propanol, isopropanol, N-methyl-2-pyrrolidone, and the like. The alkali concentration of the developer is usually 0.01 to 20 wt%, preferably 0.02 to 10 wt%, and the temperature of the developer is usually 0 to 80 ℃, preferably 10 to 60 ℃. The developed relief pattern is preferably washed with a washing solution such as water or an acidic aqueous solution.
By heat curing after development by heat treatment, a cured film having high heat resistance can be obtained because a thermally crosslinked network based on the above-mentioned components (a) and (C) is formed. The thickness of the cured film is determined by taking the thickness of the wiring into consideration, and is, for example, about 2 to 50 μm.
The curing temperature (maximum temperature at the time of thermal curing) is preferably 100 to 250 ℃, more preferably 120 to 200 ℃, and still more preferably 130 to 180 ℃ from the viewpoint of sufficiently performing thermal curing and suppressing oxidation of the metal wiring due to heat.
The cured film obtained from the photosensitive resin composition has a resolution of, for example, about 10 to 1000 μm, and thus can be suitably used as a surface protective material for a printed wiring board. Further, since the cured film is excellent in flexibility, it can be suitably used as a cured film for a flexible printed wiring board provided with a metal wiring on a flexible film such as a polyimide film. The photosensitive resin composition can also be used for forming various wiring coating protective materials, photosensitive heat-resistant adhesives, wire/cable insulating films, and the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[ Synthesis examples ]
In the following synthesis examples, (a1) was polymerized with a polymer having a carboxyl group and no photopolymerizable functional group. The properties of the solutions and polymers obtained in Synthesis examples 1 to 3 were evaluated by the following methods.
< concentration of solid content >
Measured according to JIS K5601-1-2. The drying conditions were set at 170 ℃ for 1 hour.
< weight average molecular weight >
The measurement was performed by Gel Permeation Chromatography (GPC) under the following conditions.
The using device comprises the following steps: HLC-8220GPC equivalent available from Tosoh corporation
Column: tosoh corporation TSK gel Super AWM-H (6.0mm I.D.. times.15 cm). times.2
Protection of the column: tosoh corporation TSK guard column Super AW-H
Eluent: 30mM LiBr +20mM H3PO4in DMF
Flow rate: 0.6mL/min
Column temperature: 40 deg.C
Detection conditions are as follows: RI: polarity (+), response (0.5sec)
Sample concentration: about 5mg/mL
Molecular weight standards: PEG (polyethylene glycol)
< acid value >
Measured according to JIS K5601-2-1.
(Synthesis example 1)
100.0g of methyltriglyme (1, 2-bis (2-methoxyethoxy) ethane) as a polymerization solvent was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen inlet tube, and the temperature was raised to 80 ℃ while stirring under a nitrogen stream. 12.0g (0.14 mol) of methacrylic acid, 28.0g (0.16 mol) of benzyl methacrylate, 60.0g (0.42 mol) of butyl methacrylate, and 0.5g of azobisisobutyronitrile as a radical polymerization initiator, which were previously mixed at room temperature, were added dropwise from a dropping funnel over 3 hours while maintaining the temperature at 80 ℃. After the completion of the dropwise addition, the reaction solution was heated to 90 ℃ with stirring, and further stirred for 2 hours while keeping the temperature of the reaction solution at 90 ℃ to obtain a solution of an acrylic polymer (A1-1) having a carboxyl group in the molecule. The solution had a solid content of 50%, the weight-average molecular weight of the polymer was 48000, and the acid value was 78 mgKOH/g.
(Synthesis example 2)
30.00g of methyltriglyme and 10.31g (0.050 mol) of norbornene diisocyanate as polymerization solvents were put into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen inlet tube, and dissolved by heating to 80 ℃ while stirring under a nitrogen stream. To the solution, a solution prepared by dissolving 30.00g of methyl triglyme (trade name: PCDL T5652, weight average molecular weight 2000, manufactured by Asahi chemical Co., Ltd.) in 50.00g (0.025 mol) and 3.70g (0.025 mol) of 2, 2-bis (hydroxymethyl) butyric acid was added dropwise from a dropping funnel over 1 hour. This solution was heated and stirred at 80 ℃ for 5 hours to obtain a solution of a urethane polymer (A1-2) having a carboxyl group in the molecule. The solution had a solid content of 52%, the weight-average molecular weight of the polymer was 5600, and the acid value was 22 mgKOH/g.
(Synthesis example 3)
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen inlet tube, 35.00g of methyltriglyme and 10.31g (0.050 mol) of norbornene diisocyanate as polymerization solvents were charged and dissolved by heating to 80 ℃ under stirring in a nitrogen stream. To this solution, 50.00g (0.025 mol) of polycarbonate diol dissolved in 35.00g of methyltriglyme was added dropwise from a dropping funnel over 1 hour, and after heating and stirring at 80 ℃ for 2 hours, 15.51g (0.050 mol) of 3,3 ', 4,4' -oxydiphthalic dianhydride was added, and the mixture was heated to 190 ℃ and stirred for 1 hour. Thereafter, the mixture was cooled to 80 ℃ and 3.60g (0.200 mol) of pure water was added thereto, and the mixture was heated to 110 ℃ and refluxed for 5 hours to obtain a solution of a urethane imide polymer (A1-3) having a carboxyl group in the molecule. The solution had a solid content of 53%, the weight-average molecular weight of the polymer was 9200, and the acid value was 86 mgKOH/g.
[ preparation of resin compositions of examples, comparative examples and reference examples ]
The compositions in the formulation shown in table 1 were dissolved in methyl triglyme, stirred by a stirrer, and passed through a three-roll mill 2 times. Thereafter, defoaming was performed by a defoaming device to prepare a uniform solution. The amount of methyltriglyme as a solvent (the total solvent amount including the solvent contained in the polymer solution of the synthesis example) was 60 parts by weight based on 100 parts by weight of the total (solid content) of the components (a) to (C). In addition to the components shown in Table 1, 0.2 part by weight of a butadiene-based antifoaming agent ("Flowsen AC-2000", Kyoeisha chemical Co., Ltd.) was added to each resin composition.
[ formation and evaluation of cured film ]
< photosensitivity >
A photosensitive resin composition was cast/coated on a polyimide film (manufactured by Kazakh corporation, national chemical Co., Ltd. "Apical 25 NPI") having a thickness of 25 μm to an area of 100mm × 100mm in such a manner that the final dry thickness became 20 μm using a Becker type applicator, and dried at 80 ℃ for 20 minutes, and a negative photomask having a line/space of 100 μm/100 μm was placed, and irradiated with 300mJ/cm using a high-pressure mercury lamp2After exposure with the cumulative exposure dose of ultraviolet light, 1.0kgf/mm2The aqueous solution of sodium carbonate (30 ℃ C.) having a concentration of 1.0 wt% was sprayed for 90 seconds under the above-mentioned spray pressure to develop the image. After washing with pure water, the resultant was heated in an oven at 150 ℃ for 30 minutes to cure the resin, thereby producing a patterned cured film (relief pattern) of the photosensitive resin composition.
The relief patterns formed using the compositions of examples, reference examples, and comparative examples were observed using an optical microscope, and it was found that, when any of the compositions was used, no significant line coarsening or development residue of the pattern was observed, and a photosensitive pattern of line/space of 100/100 μm appeared.
< Heat resistance >
A copper foil of a flexible copper-clad laminate in which a polyimide film (hereinafter, referred to as "additive 25 NPI" by "kokukusha corporation) having a thickness of 25 μm and an electrolytic copper foil having a thickness of 12 μm were bonded to each other with a polyimide adhesive was etched into a stripe pattern having a line/space of 100 μm/100 μm, and the resulting laminate was immersed in a 10 vol% sulfuric acid aqueous solution for 1 minute to perform surface treatment of the copper foil, followed by cleaning with pure water to produce a flexible printed board. The photosensitive resin composition is cast/coated, dried, exposed, developed, and cured by heating in the same manner as described above, thereby forming a cured film on a flexible printed board. In addition, the entire surface is irradiated with ultraviolet light without using a photomask.
The sample was immersed in a solder bath for 10 seconds, then pulled up, subjected to appearance observation and tape peeling test, and evaluated by the following criteria. The temperature of the solder bath in evaluation 1 was set to 320 ℃, and the temperature of the solder bath in evaluation 2 was set to 350 ℃.
O: no appearance change before and after the test, and the cured film was not peeled off in the tape peeling test
And (delta): no change in appearance, but peeling of the cured film in the tape peeling test
X: after the test, the appearance change such as swelling and peeling of the cured film was confirmed
< flexibility >
A photosensitive resin composition was cast/coated on a polyimide film (manufactured by Kazakh corporation, national chemical Co., Ltd. "application 25 NPI") having a thickness of 25 μm so that the final dry thickness became 20 μm, to an area of 100 mm. times.100 mm, using a Becker type applicator, and dried at 80 ℃ for 20 minutes. The test piece was cut into a size of 15mm × 100mm, exposed, developed, and cured by heating in the same manner as described above to form a cured film on the polyimide film, thereby producing a sample for flexibility evaluation.
The test specimen for evaluation was bent 180 ° with the cured film on the outside, and a load of 200g was applied to the bent position for 3 seconds. After the load was removed, the bent position was visually observed to evaluate the presence or absence of cracks. This operation was carried out until cracks occurred in the cured film, and the number of times of cracks not occurring was regarded as the number of times of folding endurance. For example, when cracking occurred in the 2 nd test, the number of folding endurance was 1.
The compounding ratios of the photosensitive resin compositions of examples, reference examples and comparative examples and the evaluation results of the cured films are shown in table 1 in a list form. The numerical values of the respective components in the table are the blending amounts (parts by weight) assuming that the total of the components (a) to (C) (resin component) is 100 parts by weight, and the details of the respective components are shown below.
(1) KaYARAD UXE-3000 manufactured by Nippon Kayaku Co., Ltd.: carbitol acetate diluent (weight average molecular weight 10000, acid value 98mgKOH/g) of acid-modified epoxy acrylate having urethane skeleton
(2) "KAYARAD CCR-1235" manufactured by Nippon Kagaku K.K.: carbitol acetate/solvent naphtha dilution of acid modified epoxy acrylate resin with cresol novolac backbone (weight average molecular weight 8000, acid number 80mgKOH/g)
(3) "KAYARAD DPHA" manufactured by Nippon Kagaku K.K.: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
(4) "GENOMER 4297" by Rahn: aliphatic urethane methacrylate (weight average molecular weight 400 to 600)
(5) "jER 828" manufactured by mitsubishi chemical corporation: bisphenol A type epoxy resin (average molecular weight 370, epoxy equivalent 190)
(6) ADEKA "Adekastab CDA-1": n- (2H-1,2, 4-triazol-5-yl) salicylamide
(7) ADEKA "Adekastab CDA-10": n' -bis {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl } hydrazine
(8) BASF "Irgacure OXE 02": ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime); absorbance at wavelength 405nm of 0.001% methanol solution: 0.002
(9) Manufactured by ADEKA "ADEKA ARKLS NCI-831": nitro-substituted carbazole oxime ester photo-free radical polymerization initiator; absorbance at wavelength 405nm of 0.001% methanol solution: 0.03
(10) Black colorant: the weight ratio of 1: 1: 1A colorant obtained by mixing the following blue colorant, orange colorant and violet colorant
Blue colorant: "GLVO" by BASF; fragment Blue 15: 3
Orange colorant: "GRL" manufactured by Clariant; pigment Orange 43
Purple colorant: "ER-02" manufactured by Clariant; pigment Violet 19
[ Table 1]
Figure BDA0002639895880000261
The cured film of comparative example 1 containing no component (D) (metal deactivator) had poor welding heat resistance. In comparative example 2 using a photopolymerization initiator having a large absorbance at a wavelength of 405nm, the soldering heat resistance at 320 ℃ was improved as compared with comparative example 1, but the soldering heat resistance at 350 ℃ was not improved. Comparative example 3 using a composition containing no colorant exhibited higher soldering heat resistance than comparative examples 1 and 2.
In example 5 in which a benzamide derivative was added as the component (D), improvement in the soldering heat resistance was observed as compared with comparative example 1. Reference example 1 using a composition containing no colorant exhibited more excellent welding heat resistance than example 1. From these results, it can be seen that: in the composition containing a colorant, the heat resistance of the cured film tends to be lowered, but the heat resistance is improved by adding a metal deactivator.
In example 3 in which the component (E) (photopolymerization initiator) was changed to a photopolymerization initiator having an absorption band at a wavelength of 405nm, the heat resistance was further improved as compared with example 5. Examples 1,2,4, 6 to 8 using the same photopolymerization initiator as in example 3 also showed excellent heat resistance as in example 3. From these results, it can be seen that: in the photosensitive resin composition containing the colorant, a cured film having excellent heat resistance can be formed by using a metal deactivator and using a photopolymerization initiator having an absorption band at a long wavelength.
Focusing on the flexibility of the cured film, it was found that the number of folding endurance increases and the flexibility improves in example 2 using the polymer (A1-2) and example 3 using the polymer (A1-3) as the component (A1) as compared with example 1. In addition, compared with example 6 in which only the polyfunctional acrylate was used as the component (B), example 5 in which the polyfunctional acrylate and the urethane methacrylate were used in combination improved flexibility of the cured film, and the same tendency was observed in comparison between example 8 and example 7. In example 5 in which a polymer having a urethane skeleton was used as the component (a2), the flexibility of the cured film was improved as compared with example 7, and the same tendency was observed in comparison with examples 6 and 8.
From these results, it can be seen that: by using a compound having a large molecular weight (a large functional group equivalent) and a polymer (oligomer) having a urethane chain as the component (a1) and the component (B) contributing to the formation of a thermally crosslinked network and the component (a2) contributing to the formation of a photo-crosslinked network and a thermally crosslinked network, a cured film having high heat resistance and excellent flexibility can be formed.

Claims (22)

1. A photosensitive resin composition comprising:
(A1) a polymer having a carboxyl group and no ethylenically unsaturated group;
(A2) a polymer having a carboxyl group and an ethylenically unsaturated group;
(B) a compound having an ethylenically unsaturated group and having no carboxyl group;
(C) a thermosetting resin;
(D) a metal deactivator;
(E) a photopolymerization initiator; and
(F) a colorant.
2. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (E) has an absorption band at a wavelength of 405 nm.
3. The photosensitive resin composition according to claim 1 or 2, wherein the (F) colorant is a black colorant.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (F) colorant comprises an organic pigment,
the organic pigment includes 1 or more selected from the group consisting of a blue organic pigment, an orange organic pigment, a yellow organic pigment, a red organic pigment, and a violet organic pigment.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (A2) is a polymer containing at least 1 carboxyl group and 2 or more (meth) acryloyl groups in 1 molecule.
6. The photosensitive resin composition according to claim 5, wherein the (A2) is an epoxy (meth) acrylate.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) compound contains at least 2 (meth) acryloyl groups in 1 molecule.
8. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) is a polyfunctional (meth) acrylate containing 3 or more (meth) acryloyl groups in 1 molecule and having a functional group equivalent of 80 to 300.
9. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) comprises: 1 a polyfunctional (meth) acrylic compound having 3 or more (meth) acryloyl groups in a molecule and a functional group equivalent of the (meth) acryloyl group of 80 to 300, and 1 a polyfunctional (meth) acrylic oligomer having 2 or more (meth) acryloyl groups in a molecule.
10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the (C) contains a polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule.
11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the acid values of (A1) and (A2) are 5 to 200mgKOH/g, respectively, and the weight average molecular weights are 1000 to 1000000, respectively.
12. The photosensitive resin composition according to any one of claims 1 to 11, wherein the photopolymerization initiator (E) is an oxime ester.
13. The photosensitive resin composition according to any one of claims 1 to 12, wherein the metal deactivator (D) contains 1 or more selected from the group consisting of a benzamide derivative having a phenolic hydroxyl group and a hydrazide derivative having a phenolic hydroxyl group.
14. The photosensitive resin composition according to any one of claims 1 to 13, wherein the total content of (A1) and (A2) is 30 to 80 parts by weight, the content of (B) is 5 to 30 parts by weight, and the content of (C) is 10 to 40 parts by weight, based on 100 parts by weight of the total content of (A1), (A2), (B) and (C).
15. A photosensitive resin composition production kit for producing the photosensitive resin composition according to any one of claims 1 to 14,
the kit independently comprises a1 st agent and a2 nd agent,
the 1 st agent comprises the (A1) and the (A2),
said 2 nd agent comprises said (D).
16. The photosensitive resin composition production kit according to claim 15, wherein the 2 nd agent comprises the (E).
17. The photosensitive resin composition production kit according to claim 15 or 16, wherein the 2 nd agent contains the (C).
18. The photosensitive resin composition production kit according to any one of claims 15 to 17, wherein the 1 st agent contains the (B).
19. A cured film formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 14.
20. A printed wiring board with a cured film, which is connected to a metal wiring of a printed wiring board, and which comprises the cured film according to claim 19.
21. The cured film-bearing printed circuit board of claim 20, wherein the printed circuit board has flexibility.
22. A method for producing a printed wiring board with a cured film, comprising applying the photosensitive resin composition according to any one of claims 1 to 14 to a metal wiring forming surface of a printed wiring board to form a coating film,
at least a part of the surface of the coating film is irradiated with active light to be photo-cured,
the coating film after photocuring is heated to be thermally cured.
CN201980014187.1A 2018-02-19 2019-02-15 Photosensitive resin composition, cured film, printed wiring board and method for producing same, and photosensitive resin composition production kit Pending CN111758073A (en)

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