CN114945611A - Curable composition, dry film thereof, and cured product thereof - Google Patents

Curable composition, dry film thereof, and cured product thereof Download PDF

Info

Publication number
CN114945611A
CN114945611A CN202180008557.8A CN202180008557A CN114945611A CN 114945611 A CN114945611 A CN 114945611A CN 202180008557 A CN202180008557 A CN 202180008557A CN 114945611 A CN114945611 A CN 114945611A
Authority
CN
China
Prior art keywords
epoxy resin
resin
curable composition
group
bisphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202180008557.8A
Other languages
Chinese (zh)
Inventor
车河那
福田晋一朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of CN114945611A publication Critical patent/CN114945611A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
    • 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
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)

Abstract

[ problem ] to provide: a curable composition capable of forming a solder resist layer having both solder flux resistance and bendability. [ solution ] A curable composition containing: (A) an alkali-soluble resin having at least any one structure of a bisphenol a structure, a bisphenol F structure, and a urethane structure; (B) a photopolymerization initiator; and, (C) an epoxy resin having an isocyanurate structure; the epoxy resin having an isocyanurate structure (C) has a structure in which a nitrogen atom and an epoxy group in the isocyanurate structure are bonded to each other through an alkylene chain having 2 or more carbon atoms.

Description

Curable composition, dry film thereof, and cured product thereof
Technical Field
The present invention relates to a curable composition, and particularly to a curable composition capable of forming a cured product having both flux resistance and bendability.
Background
Conventionally, a solder resist layer (SR) is formed on a printed circuit board to protect a circuit, and a semiconductor chip or the like is soldered (mounted) on the printed circuit board on which the solder resist layer is formed. Examples of the composition for forming such a solder resist layer include: a solder resist ink for circuit boards, which contains a photosensitive resin composition containing a carboxyl group-containing photosensitive polymer as a base, described in patent document 1.
On the other hand, in soldering, a flux is generally applied to the surface of a connecting circuit, but in the application step, the flux is exposed to the entire surface of the printed circuit board on which the solder resist layer is formed. The flux is used for removing oxides and pollutants on the circuit connecting surface, preventing oxidation in the heating process, and further has the effects of reducing the surface tension of molten solder and enabling the solder to well wet the joint part.
On the other hand, if the frequency of use of a so-called flexible printed circuit board is increased in view of the use of the printed circuit board in bending, flexibility to the extent that the solder resist layer formed on the printed circuit board can withstand bending is also required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 11-65117
Disclosure of Invention
Problems to be solved by the invention
That is, the solder resist layer is required to have flux resistance, that is, the following properties: even in the high temperature treatment of soldering after the flux is applied, the adhesion with the printed circuit board is maintained and the printed circuit board is not peeled off. In addition, the solder resist layer is required to have a bending property that does not cause cracking even when the printed wiring board is bent.
However, in this regard, a solder resist layer obtained from the conventional composition described in patent document 1 is easily deteriorated by flux components and is insufficient in flexibility, and therefore it is difficult to achieve both flux resistance and bendability.
Means for solving the problems
Therefore, in view of the above-mentioned aspects, the present inventors have conducted intensive studies and, as a result, have found that: the present inventors have found that a curable composition containing an alkali-soluble resin having a bisphenol a structure or the like and an epoxy resin having a specific structure having both an isocyanurate structure and an alkylene structure can form a solder resist layer having both solder flux resistance and bendability, and have completed the present invention.
That is, the present invention relates to a curable composition containing:
(A) an alkali-soluble resin having at least any one structure of a bisphenol a structure, a bisphenol F structure, and a urethane structure;
(B) a photopolymerization initiator; and (c) and (d),
(C) an epoxy resin having an isocyanurate structure, wherein,
the epoxy resin having an isocyanurate structure (C) has a structure in which a nitrogen atom and an epoxy group in the isocyanurate structure are bonded to each other through an alkylene chain having 2 or more carbon atoms.
A preferred embodiment of the present invention relates to a curable composition further containing a powder or a crystalline epoxy resin, preferably an epoxy resin having a biphenyl structure.
Further, a more preferred embodiment of the present invention relates to a curable composition further containing an epoxy resin having a dicyclopentadiene structure.
A more preferred embodiment of the present invention relates to a curable composition, wherein the mass ratio of the epoxy resin having an isocyanurate structure (C) to the epoxy resin having a dicyclopentadiene structure (C) to the powder or crystalline epoxy resin is 1: 2-6: 1 to 3.
Further, a more preferred embodiment of the present invention relates to a curable composition further containing urethane beads and/or epoxidized polybutadiene.
A more preferred embodiment of the present invention relates to a curable composition further containing a cellulose resin.
Another embodiment of the present invention relates to: a dry film having a resin layer obtained from the curable composition; a cured product obtained by curing the curable composition or the resin layer of the dry film; and an electronic component having the cured product.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there is provided: a curable composition capable of forming a solder resist layer having excellent solder flux resistance and bendability.
Detailed Description
Hereinafter, each component constituting the curable composition of the present invention will be described.
[ (A) alkali-soluble resin ]
The alkali-soluble resin (a) used in the present invention has at least any one of a bisphenol a structure, a bisphenol F structure and a urethane structure, and may be used in combination with alkali-soluble resins having structures other than these structures, as will be described later.
(A) The alkali-soluble resin is a resin which contains 1 or more functional groups selected from a phenolic hydroxyl group, a mercapto group and a carboxyl group and is soluble in an alkali solution, and preferable examples thereof include a compound having 2 or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having 2 or more mercapto groups. As the alkali-soluble resin, a carboxyl group-containing resin or a phenol hydroxyl group-containing resin can be used, but a carboxyl group-containing resin is preferable.
The carboxyl group-containing resin can exhibit alkali developability by containing a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable that the resin has an ethylenically unsaturated group in the molecule in addition to the carboxyl group, and only a carboxyl group-containing resin having no ethylenically unsaturated group may be used. As the ethylenically unsaturated group, those derived from acrylic acid or methacrylic acid or their derivatives are preferred. Among the carboxyl group-containing resins, preferred are: a carboxyl group-containing resin having a urethane structure, a carboxyl group-containing resin obtained by using a bisphenol a type epoxy resin or a bisphenol F type epoxy resin as a starting material, and a carboxyl group-containing resin obtained by using bisphenol a or bisphenol F as a starting material. Specific examples of the carboxyl group-containing resin include the following compounds (both oligomers and polymers).
(1) A carboxyl group-containing photosensitive resin obtained by reacting a bisphenol a type epoxy resin or a bisphenol F type epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to a hydroxyl group present in a side chain. Here, the polyfunctional epoxy resin of 2 functions or more is preferably a solid.
(2) A carboxyl group-containing photosensitive resin obtained by further epoxidizing the hydroxyl group of a bisphenol a type epoxy resin or a bisphenol F type epoxy resin with epichlorohydrin to obtain a polyfunctional epoxy resin, reacting the obtained polyfunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl group. Here, the 2-functional epoxy resin is preferably a solid.
(3) A carboxyl group-containing photosensitive resin obtained by reacting a bisphenol a type epoxy resin or a bisphenol F type epoxy resin with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, or the like.
(4) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a condensate of bisphenol a or bisphenol F and an aldehyde with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(5) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting bisphenol a or bisphenol F with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid and reacting the obtained reaction product with a polybasic acid anhydride.
(6) A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and reacting the terminal of the obtained urethane resin with an acid anhydride.
(7) In the synthesis of a carboxyl group-containing urethane resin by the polyaddition reaction of a diol compound and a diol compound containing a carboxyl group such as diisocyanate and dimethylolpropionic acid or dimethylolbutyric acid, a carboxyl group-containing urethane resin in which the terminal is (meth) acrylated by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added.
(8) In the synthesis of a carboxyl group-containing urethane resin obtained by the polyaddition reaction of a diisocyanate, a carboxyl group-containing diol compound and a diol compound, a carboxyl group-containing urethane resin having a terminal (meth) acryloyl group by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in a molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate.
(9) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to any of the carboxyl group-containing resins (1) to (8).
(A) As the alkali-soluble resin having a structure other than the alkali-soluble resin, the following compounds (both oligomers and polymers) can be exemplified.
(10) A carboxyl group-containing photosensitive resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.
(11) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional oxetane resin described later with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to add a dibasic acid anhydride to the generated primary hydroxyl group to obtain a carboxyl group-containing polyester resin, and further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate to the obtained carboxyl group-containing polyester resin.
(12) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to the carboxyl group-containing resin of the above (10) or (11).
Here, (meth) acrylate refers to a term collectively referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.
Here, the carboxyl group-containing resin preferably has an acid value of 40 to 150 mgKOH/g. The acid value of the carboxyl group-containing resin is preferably 40mgKOH/g or more, whereby alkali development is preferably performed. In addition, by setting the acid value to 150mgKOH/g or less, a normal resist pattern can be easily drawn. More preferably 50 to 130 mgKOH/g.
The amount of the alkali-soluble resin (A) is preferably 15 to 35% by mass of the total composition. When 15 to 35% by mass, the coating film strength is good, the viscosity of the composition is moderate, and the coating property is improved.
[ (B) photopolymerization initiator ]
The photopolymerization initiator (B) may be any known photopolymerization initiator or photo radical generator, and examples thereof include: bis- (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -1-naphthylphosphine oxide, bisacylphosphine oxides such as bis- (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 5-dimethylphenylphosphine oxide, and bis- (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; monoacyl phosphine oxides such as 2, 6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphine oxide and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; hydroxyacetophenones such as 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, michelson, methylbenzophenone, 4 '-dichlorobenzophenone, 4' -bisdiethylaminobenzophenone and the like; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl) -1- [4- (4-morpholino) phenyl ] -1-butanone, N-dimethylaminoacetophenone and the like; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, and ethyl p-dimethylbenzoate; oxime esters such as 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime) and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetoxime); titanocenes such as bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (2- (1-pyrrol-1-yl) ethyl) phenyl ] titanium, and the like; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. The photopolymerization initiator may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
(B) The amount of the photopolymerization initiator is preferably 8 to 15 parts by mass per 100 parts by mass of the alkali-soluble resin (A). When the amount is within this range, the surface curability is good, halation is less likely to occur, and good resolution can be obtained.
[ (C) epoxy resin having isocyanurate Structure ]
The curable composition of the present invention contains the following epoxy resin: the epoxy resin has an isocyanurate structure in which a nitrogen atom and an epoxy group are bonded to each other by an alkylene chain having 2 or more carbon atoms. Particularly preferred is an epoxy resin having a structure in which the number of carbons in the alkylene chain is 2 or more and 5 or less. When the number of carbon atoms in the alkylene chain is within the range of 2 to 5, the flux resistance and the bending property are effective in a cured product obtained from the curable composition. In addition, the original developability of the curable composition can be maintained.
The epoxy resin having an isocyanurate structure (C) used in the present invention preferably has a structure represented by the following formula (I).
Figure BDA0003734590670000071
(in the formula (1),
R 1 、R 2 and R 3 Each independently represents an alkylene group having 2 to 5 carbon atoms,
n is 0 or 1, but all n do not simultaneously represent 0)
Among them, particularly preferred are: in the formula (1), R 1 、R 2 And R 3 And n represents an alkylene group having 3 carbon atoms and 1.
Specific examples of the epoxy resin having an isocyanurate structure (C) preferably used in the present invention include TEPIC (registered trademark) -VL and TEPIC (registered trademark) -FL (all manufactured by nippon chemical industries).
The amount of the epoxy resin having an isocyanurate structure (C) is preferably 5 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the content is within this range, good flux resistance and bending property can be imparted to the cured product at the same time, and the original developability of the curable composition can be maintained.
[ inorganic Filler ]
The curable composition of the present invention may contain an inorganic filler for the purpose of suppressing curing shrinkage, and improving properties such as adhesion and hardness.
The inorganic filler is not particularly limited, and known and commonly used fillers, for example, inorganic fillers such as silica, crystalline silica, noni's silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminosilicate, calcium silicate, and zinc oxide can be used. Among these, silica is preferable, and spherical silica is more preferable in terms of small surface area and less tendency to become a starting point of a crack because stress is dispersed throughout the entire silica.
The inorganic filler may be subjected to a photoreactive surface treatment to have a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, or the like as a photocurable reactive group, and in this case, a methacryloyl group, an acryloyl group, and a vinyl group are particularly preferable. The thermally reactive surface treatment may be carried out to have a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group or the like as a thermosetting reactive group, and in this case, an amino group or an epoxy group is particularly preferable. Further, the inorganic filler may have 2 or more kinds of curable reactive groups. As the inorganic filler, surface-treated silica is preferable. By including surface-treated silica, the CTE can be lowered and the glass transition temperature can be raised.
The method for introducing the curable reactive group to the surface of the inorganic filler is not particularly limited, and the curable reactive group can be introduced by a known and commonly used method, and the surface of the inorganic filler can be treated with a surface treating agent having a curable reactive group, for example, a coupling agent having a curable reactive group.
As the surface treatment of the inorganic filler, surface treatment with a coupling agent is preferable. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Among them, a silane coupling agent is preferable.
The silane coupling agent is preferably a silane coupling agent capable of introducing a curing reactive group into the inorganic filler. Examples of the silane coupling agent capable of introducing a thermosetting reactive group include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having an isocyanate group, and among these, a silane coupling agent having an epoxy group is more preferable. The silane coupling agent capable of introducing the photocurable reactive group is preferably a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacryloyl group, or a silane coupling agent having an acryloyl group, and more preferably a silane coupling agent having a methacryloyl group.
When the inorganic filler is surface-treated, it may be mixed in the curable resin composition of the present invention in a surface-treated state, and the inorganic filler may be surface-treated by separately mixing the inorganic filler whose surface is not treated and the surface treatment agent, but it is preferable to previously mix the inorganic filler whose surface is treated. By compounding the inorganic filler subjected to surface treatment in advance, it is possible to prevent the deterioration of crack resistance and the like due to the surface treatment agent that may remain in the case of compounding separately and that is not consumed in the surface treatment. When the surface treatment is performed in advance, a predispersion solution in which an inorganic filler is predispersed in a solvent or a resin component is preferably blended, and more preferably: predispersing the surface-treated inorganic filler in a solvent, and compounding the predispersion with a composition; alternatively, the surface treatment may be sufficiently performed when the inorganic filler having an untreated surface is predispersed in a solvent, and then the predispersion solution may be mixed with the composition.
In the curable composition of the present invention, the inorganic filler preferably has an average particle diameter of 1 μm or less, from the viewpoint of further excellent crack resistance. More preferably 0.8 μm or less. In the present specification, the average particle diameter means D 50 The value of (b) is measured, for example, by using a Microtrac particle size analyzer manufactured by Nikkiso K.K.
In addition, the maximum particle size of the inorganic filler is preferably 4.0 μm or less from the viewpoint of efficiently performing the reaction and further excellent crack resistance and adhesion. More preferably 3.0 μm or less. In the present specification, the maximum particle diameter means D 100 The value of (b) is measured, for example, by using a Microtrac particle size analyzer manufactured by Nikkiso K.K.
When the curable composition of the present invention contains an inorganic filler, the amount of the inorganic filler to be blended is preferably 15 to 35 parts by mass based on 100 parts by mass of the solid content of the curable composition.
[ powder or crystalline epoxy resin ]
The curable composition of the present invention preferably contains an epoxy resin, and particularly preferably contains a powder or a crystalline epoxy resin. This further improves the flux resistance of the cured product.
The powder or crystalline epoxy resin means: the highly crystalline epoxy resin is a thermosetting epoxy resin in which polymer chains are regularly arranged at a temperature of not more than the melting point, and which is a solid resin and has a low viscosity equivalent to that of a liquid resin when melted.
As the powder or crystalline epoxy resin, a crystalline epoxy resin having any one of a biphenyl structure, a thioether structure, a phenylene structure, and a naphthylene structure is preferably used.
Biphenyl type epoxy resins are supplied, for example, as "jER (registered trademark) YX 4000", "jER (registered trademark) YX 4000H", "jER (registered trademark) YL61 6121H", "jER (registered trademark) YL 6640", "jER (registered trademark) YL 6677" manufactured by Mitsubishi Chemical Corporation, diphenyl sulfide type epoxy resins are supplied, for example, as NIPPON STEEL Chemical & Material Co., manufactured by Ltd "," Epotoo (registered trademark) YSLV-120TE "manufactured by Ltd, phenylene type epoxy resins are supplied, for example, as" EPICLON (registered trademark) HP-2 "," EPICLON (registered trademark) HP-4032 "," EPICLON (registered trademark) HP-4700 "manufactured by Nippon STEEL Chemical & Material Co., manufactured by Ltd. Further, NIPPON STEEL Chemical & Material Co., Ltd., "Epototo (registered trademark) YSLV-90C" manufactured by Ltd., and "TEPIC-S" (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd., can be used as the powder or the crystalline epoxy resin. Among them, for excellent solder heat resistance characteristics, "jER (registered trademark) YX 4000" manufactured by Mitsubishi Chemical Corporation as a biphenyl type epoxy resin is preferable.
In the curable composition of the present invention, 1 or 2 or more of these powder or crystalline epoxy compounds may be used alone or in combination.
The amount of such powder or crystalline epoxy resin to be blended is preferably 20 to 40 parts by mass based on the solid content relative to 100 parts by mass of the alkali-soluble resin (A).
When the amount of the powder or the crystalline epoxy resin is in the above range, the developability and the flux resistance are further improved.
The curable composition of the present invention may further contain an epoxy resin other than the powdery or crystalline epoxy resin for the purpose of improving heat resistance.
Examples of such epoxy resins include: non-crystalline cresol novolak-type epoxy resin (trade name EPICLON N-695 manufactured by DIC Corporation as a specific example), non-crystalline phenol novolak-type epoxy resin (trade name EPICLON N-775 manufactured by DIC Corporation as a specific example), non-crystalline bisphenol A novolak-type epoxy resin (trade name EPICLON N-865 manufactured by DIC Corporation as a specific example), non-crystalline bisphenol A-type epoxy resin (trade name jER1001 manufactured by Mitsubishi Chemical Corporation as a specific example), non-crystalline bisphenol F-type epoxy resin (trade name j4004P manufactured by Mitsubishi Chemical ER Corporation as a specific example), non-crystalline bisphenol S-type epoxy resin (trade name EPLON EXA-1514 manufactured by Mitsubishi Chemical Corporation as a specific example), non-crystalline bisphenol AD-type epoxy resin, non-crystalline hydrogenated bisphenol A-type epoxy resin, and epoxy resin, Non-crystalline bisphenol aldehyde varnish type epoxy resins, and non-crystalline special bifunctional epoxy resins (trade names YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; trade names EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822 and EPICLON EXA-9726, which are specific examples of the non-crystalline epoxy resins.
Or there may be mentioned: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, or phenol novolac type epoxy resin. Specific examples of the liquid epoxy resin include liquid epoxy resins such as "EXA 4032 SS", "HP 4032 SS", "EXA-7311G 4S" (naphthalene-based epoxy resin), and "jER 828 EL" (bisphenol A-type epoxy resin), and "jER 807" (bisphenol F-type epoxy resin), and "jER 152" (phenol novolac-type epoxy resin), and "YL 7223" and "77YL 23" (bisphenol AF-type epoxy resin), which are manufactured by DIC Corporation.
Further, there may be mentioned a 4-functional naphthylene type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol epoxy resin, a naphthol novolak type epoxy resin, a biphenyl type epoxy resin, or a solid epoxy resin such as a naphthyl ether type epoxy resin. Among them, a 4-functional naphthylene type epoxy resin, a biphenyl type epoxy resin, or a naphthalene ether type epoxy resin is more preferable, and a biphenyl type epoxy resin is further preferable. Specific examples of such solid epoxy resins include "HP-4710" (4-functional naphthylene type epoxy resin), "EXA 7311", "EXA 7311-G3", "HP 6000" (naphthalene ether type epoxy resin), "EPPN-502H" (triphenol epoxy resin), "NC 7000L" (naphthol novolac epoxy resin), "NC 3000H", "NC 3000L", "NC 3100" (biphenyl type epoxy resin), NIPPON STEEL Chemical & Material co., ltd., "ESN 475", "ESN" (naphthol novolac type epoxy resin), and "biphenyl type epoxy resin", manufactured by Mitsubishi Chemical Corporation.
In the curable composition of the present invention, the epoxy resin other than the powdery or crystalline epoxy resin preferably contains an epoxy resin having a dicyclopentadiene structure. Examples of such epoxy resins include "HP 7200", "HP 7200H", "HP 7200K" and "HP 7200L" manufactured by DIC corporation.
The mass ratio of the epoxy resin having an isocyanurate structure (C) to the epoxy resin having a dicyclopentadiene structure (C) to the powdery or crystalline epoxy resin is particularly preferably 1: 2-6: 1 to 3. When the amount is within this range, the curable composition of the present invention can exhibit the optimum flux resistance and bending property.
The mixing ratio of the powder or crystalline epoxy resin to the other epoxy resins is preferably 5: 1-1: 5 in the above range.
[ urethane bead/epoxidized polybutadiene ]
In the curable composition of the present invention, urethane beads and/or epoxidized polybutadiene are preferably contained in order to improve flexibility. In particular, by containing epoxidized polybutadiene, the flexibility of the cured product becomes better.
The amount of urethane beads to be mixed is preferably 20 to 35 parts by mass based on 100 parts by mass of the alkali-soluble resin (a).
The amount of the epoxidized polybutadiene to be blended is preferably 8 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (a).
[ cellulose resin ]
The curable composition of the present invention preferably contains a cellulose resin.
By containing the cellulose resin, the amount of liquid components (for example, liquid epoxy resin, monomer component) can be increased, and thus flux resistance can be easily ensured. In addition, the effect of suppressing stickiness (stickiness) at the time of exposure is also exhibited.
The amount of the cellulose resin to be blended is preferably 5 to 10 parts by mass based on 100 parts by mass of the alkali-soluble resin (a).
[ coloring agent ]
The curable composition of the present invention may contain a colorant. Specific examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, leuco crystal violet, carbon black, naphthalene black, solvent blue, and the like. The colorant may be used in 1 kind, or 2 or more kinds may be used in combination.
The amount of the colorant added is not particularly limited, and is preferably in a proportion of 7 to 15 parts by mass per 100 parts by mass of the alkali-soluble resin (A).
[ organic solvent ]
The curable composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like.
As such an organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and known and commonly used organic solvents such as petroleum solvents including petroleum ether, petroleum naphtha, solvent naphtha, and the like. These organic solvents may be used alone or in combination of two or more.
[ Compound having an ethylenically unsaturated group ]
The curable composition of the present invention preferably further contains a compound having an ethylenically unsaturated group as a reactive diluent. Examples of the compound having an ethylenically unsaturated group include compounds having a monofunctional (meth) acryloyl group, a 2-functional (meth) acryloyl group, and the like.
Examples of the monofunctional (meth) acryloyl group compound include: aliphatic (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, butoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, and glycerol mono (meth) acrylate, cyclohexyl (meth) acrylate, 4- (meth) acryloyloxytetracyclo [5.2.1.02,6] decane, alicyclic (meth) acrylates such as isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, aromatic (meth) acrylates such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like, and mixtures thereof, Modified (meth) acrylates such as aliphatic epoxy-modified (meth) acrylates, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyalkyl phosphate, 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl phthalate, γ - (meth) acryloyloxyalkyltrialkoxysilane, and the like.
Specific examples of the compound having a 2-functional (meth) acryloyl group include 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate and other diol diacrylates, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, diol diacrylate obtained by adding at least 1 of ethylene oxide and propylene oxide to neopentyl glycol, caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate and other diol diacrylates, bisphenol A EO adduct diacrylates, bisphenol A EO adducts, and mixtures thereof, And diacrylates having a cyclic structure such as bisphenol A PO adduct diacrylate, tricyclodecane dimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, and cyclohexyl diacrylate.
Specific examples of the compound having a 3-or more-functional (meth) acryloyl group include alkylene polyol poly (meth) acrylates such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; polyoxyalkylene glycol poly (meth) acrylates such as propoxylated trimethylolpropane tri (meth) acrylate, and the like.
The amount of the compound having an ethylenically unsaturated group to be blended is preferably 20 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a).
[ Heat curing catalyst ]
The curable composition of the present invention may contain a thermosetting catalyst for improving storage stability and heat resistance.
Examples of such a thermosetting catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and the like. Further, s-triazine derivatives such as guanamine, methylguanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine/isocyanuric acid adduct, and 2, 4-diamino-6-methacryloyloxyethyl-s-triazine/isocyanuric acid adduct may be used.
The amount of the thermosetting catalyst is preferably 2.0 to 4.5 parts by mass per 100 parts by mass of the alkali-soluble resin (A).
[ other ingredients ]
Other additives commonly used in the field of electronic materials may be further blended in the curable composition of the present invention. Examples of the other additives include a thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/antifungal agent, a leveling agent, a thickener, an adhesion imparting agent, a thixotropy imparting agent, a photo-initiation aid, a sensitizer, a photobase generator, an organic filler such as a thermoplastic resin and further an elastomer, a release agent, a surface treating agent, a dispersant, a dispersing aid, a surface modifier, a stabilizer, and a phosphor.
[ Dry film ]
The curable composition of the present invention may be used in the form of a dry film. The dry film of the present invention has a resin layer obtained by applying the curable composition of the present invention on a carrier film and drying the same.
In forming a dry film, the curable composition of the present invention is first diluted with the above-mentioned organic solvent, adjusted to an appropriate viscosity, and then applied to a carrier film in a uniform thickness by means of a comma coater, a blade coater, a lip coater, a bar coater, a press coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like. Thereafter, the coated composition is dried at a temperature of 40 to 130 ℃ for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, and is usually selected appropriately within a range of 3 to 150 μm, preferably 5 to 60 μm, in terms of the film thickness after drying.
As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, and is usually suitably selected within the range of 10 to 150 μm. More preferably 15 to 130 μm.
After forming a resin layer containing the curable composition of the present invention on a carrier film, a releasable protective film is preferably further laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. Examples of the peelable protective film include a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and surface-treated paper. The protective film may be a film that is peeled off with less adhesion than the resin layer and the carrier film.
In the present invention, the curable composition of the present invention may be applied to the protective film and dried to form a resin layer, and the carrier film may be laminated on the resin layer. That is, in the production of the dry film of the present invention, any of a carrier film and a protective film may be used as a film to which the curable composition of the present invention is applied.
[ cured product ]
When a cured product is formed using the curable composition of the present invention, the composition is applied to a substrate, a solvent is evaporated and dried to obtain a resin layer, and the obtained resin layer is exposed (irradiated with light) to cure an exposed portion (portion after the light irradiation). Specifically, a resist pattern is formed by selectively exposing a photomask having a pattern formed thereon with an active energy ray by a contact or non-contact method, or directly exposing the pattern with a laser direct exposure machine, and developing the unexposed portion with an aqueous alkali solution (for example, an aqueous sodium carbonate solution of 0.3 to 3 mass%) to form a resist pattern. And further heated to a temperature of about 100 to 180 ℃ to be thermally cured (post-cured), whereby a cured coating (cured product) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.
The curable composition of the present invention can be formed into a tack-free resin layer by, for example, adjusting the viscosity to a viscosity suitable for a coating method using the organic solvent, applying the composition onto a substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method, and then evaporating and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ℃. In the case of a dry film obtained by applying the curable composition to a support film or a protective film, drying the composition, and winding the film, the resin layer can be laminated on a substrate by laminating the dry film of the present invention on the substrate so that the resin layer is in contact with the substrate using a laminator or the like, and then peeling the support film.
Examples of the base material include a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance with copper or the like, and further include: copper-clad laminates of all grades (FR-4 and the like) using materials such as paper phenol resins, paper epoxy resins, glass cloth epoxy resins, glass polyimides, glass cloth/nonwoven fabric epoxy resins, glass cloth/paper epoxy resins, synthetic fiber epoxy resins, fluorine resin/polyethylene/polyphenylene ether, polyphenylene ether/cyanate esters and the like for high-frequency circuits, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like.
The evaporation drying or the heat curing may be performed by using a hot air circulation type drying oven, an IR oven, a hot plate, a convection oven, or the like (a method of bringing hot air in a dryer into convection contact with a heat source using a steam-based air heating system, or a method of blowing hot air from a nozzle to a support).
The exposure machine used for the irradiation with the active energy ray may be a device that is equipped with a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiates the active energy ray in a range of 350 to 450nm, and a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) may be used. As a lamp light source or a laser light source of the line drawing machine, the maximum wavelength can be in the range of 350-410 nm. The exposure amount for image formation is usually set to 20 to 1000mJ/cm, which varies depending on the film thickness 2 Preferably 20 to 800mJ/cm 2 Within the range of (1).
The developing method may be carried out by a dipping method, a spraying method, a brush coating method, or the like, and an aqueous alkali solution such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used as the developer.
The curable composition of the present invention is suitably used for forming a surface protective film such as a solder resist layer on a flexible printed wiring board. The curable composition of the present invention can also be used as an interlayer insulating layer of a multilayer printed wiring board.
[ electronic component ]
In addition, the present invention also provides the following electronic component: the curable composition of the present invention is cured to obtain a cured product. By using the curable composition of the present invention, an electronic component having high quality, durability and reliability can be provided.
The electronic component in the present invention is a component used for an electronic circuit, and includes not only active components such as a printed circuit board, a transistor, a light emitting diode, and a laser diode, but also passive components such as a resistor, a capacitor, an inductor, and a connector, and the cured product of the present invention exhibits the effects of the present invention as the insulating cured coating film.
The flux showing excellent resistance of the cured product of the present invention relates to all conventional compositions and formulations mainly composed of rosin, and examples of such flux include SF-270, SF-360PF-1, SRM-800G (both manufactured by Sanwa Kagaku Corp.), JS-E-15X, JS-EU-31 (both manufactured by KOKI Company Ltd.), NS-F850-8, NS-F901, NS-334, NS-316F-8(Nippon Superior Co., Ltd.), and the like.
The following describes an embodiment of the present invention specifically with reference to examples, but it is needless to say that the present invention is not limited to the scope of the claims.
Examples
< Synthesis example 1. preparation of carboxyl group-containing acrylate resin (bisphenol A Structure) >
Into a flask equipped with a condenser and a stirrer, 456 parts of bisphenol A, 228 parts of water and 649 parts of 37% formaldehyde were charged, and while maintaining a temperature of 40 ℃ or lower, 228 parts of a 25% aqueous sodium hydroxide solution was added, followed by reaction at 50 ℃ for 10 hours after completion of the addition. After completion of the reaction, the reaction mixture was cooled to 40 ℃ and then neutralized to pH4 with 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ℃. Then, the mixture was allowed to stand to separate an aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed with 500 parts of distilled water 3 times, and water, a solvent and the like were removed under reduced pressure at a temperature of 50 ℃ or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
A part of the obtained methanol solution of the polymethylol compound was dried in a vacuum drier at room temperature, and as a result, the solid content was 55.2%.
Into a flask equipped with a condenser and a stirrer, 500 parts of the obtained methanol solution of the polymethylol compound and 440 parts of 2, 6-xylenol were charged and uniformly dissolved at 50 ℃. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50 ℃ or lower. Then, 8 parts of oxalic acid was added thereto, and the mixture was reacted at 100 ℃ for 10 hours. After the completion of the reaction, the fraction was removed under reduced pressure of 50mmHg at 180 ℃ to obtain 550 parts of novolak a resin.
130 parts of novolak resin a, 2.6 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene/methyl isobutyl ketone (mass ratio: 2/1) were charged into an autoclave equipped with a thermometer, an alkylene oxide introduction device serving as a nitrogen introduction device, and a stirring device, and the inside of the system was replaced with nitrogen while stirring, and then heated to 150 ℃ and 8kg/cm 2 60 parts of propylene oxide was slowly introduced to carry out the reaction. The reaction was continued for about 4 hours until the gauge pressure became 0.0kg/cm 2 After that, it was cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed, and sodium hydroxide was neutralized. The neutralized reaction product was diluted with toluene, washed with water 3 times, and desolventized in an evaporator to obtain a propylene oxide adduct of novolak a resin having a hydroxyl value of 189g/eq. Which is obtained by adding 1 mole of propylene oxide on average per 1 equivalent of phenolic hydroxyl group.
189 parts of the obtained propylene oxide adduct of novolak a resin, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 140 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, stirred while blowing air, heated to 115 ℃ while distilling off the water produced by the reaction and toluene as an azeotropic mixture, reacted for a further 4 hours, and then cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution, toluene was removed by distillation under reduced pressure, and diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
Then, 322 parts of the obtained acrylic resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were put into a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was heated to 110 ℃ and 60 parts of tetrahydrophthalic anhydride was added to carry out a reaction for 4 hours, followed by cooling and taking out. The photosensitive carboxyl group-containing resin solution thus obtained was as follows: a solid content of 70% and a solid acid value of 81 mgKOH/g.
< Synthesis example 2 preparation of carboxyl group-containing resin for comparative example >
900g of diethylene glycol dimethyl ether as a solvent and 21.4g of tert-butyl peroxy-2-ethylhexanoate (Perbutyl O, manufactured by Nippon fat Co., Ltd.) as a polymerization initiator were charged in a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and heated to 90 ℃. After heating, 309.9g of methacrylic acid, 116.4g of methyl methacrylate, and 109.8g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Ltd., Praxel FM1) and 21.4g of bis (4-t-butylcyclohexyl) peroxydicarbonate (Peroyl TCP, manufactured by Nippon oil & fat Co., Ltd.) as a polymerization initiator were added dropwise thereto over 3 hours, followed by further aging for 6 hours to obtain a carboxyl group-containing copolymer resin. The reaction was performed under a nitrogen atmosphere.
Then, 363.9g of 3, 4-epoxycyclohexylmethyl acrylate (Daicel Chemical Co., Ltd., Cyclomer A200, Ltd.) was added to the resulting carboxyl group-containing copolymer resin, 3.6g of dimethylbenzylamine as a ring-opening catalyst, and 1.80g of hydroquinone monomethyl ether as a polymerization inhibitor, and the mixture was heated to 100 ℃ and stirred to perform a ring-opening addition reaction of epoxy. After 16 hours, a solution containing 53.8% by weight (non-volatile matter) of a carboxyl group-containing resin having no aromatic ring, a solid content and an acid value of 108.9mgKOH/g and a weight-average molecular weight of 25000, was obtained.
< examples 1 to 7 and comparative examples 1 to 2 >
The curable compositions of examples 1 to 7 and comparative examples 1 to 2 were obtained by premixing the components in a mixer at the components and the amounts of the components shown in table 1 below, and then kneading the mixture by a triple roll mill.
The numerical values of the blending amounts in the tables represent parts by mass of the solid components unless otherwise specified.
[ Table 1]
TABLE 1 Components and compounding amounts of curable compositions of examples 1 to 7 and comparative examples 1 to 2
Figure BDA0003734590670000211
*1 Bisphenol F acid-modified epoxy acrylate resin, alkali-soluble resin having a bisphenol F structure (solid content 65%); ZFR-1401H; manufactured by Nippon Chemicals K.K
*2 A composite acid-modified epoxy acrylate resin and an alkali-soluble resin having a urethane structure (solid content: 52%); UXE-3000; manufactured by Nippon Chemicals K.K
*3 Synthesis example 1 above, alkali-soluble resin having bisphenol A Structure
*4 Synthesis example 2, alkali-soluble resins other than (A)
*5 CAP 504-0.2; EASTMAN CHEMICAL manufactured by Inc
*6 Dicyandiamide (Dicyandiamide); manufactured by Mitsubishi Chemical Corporation
*7 Paliogen Red K3580; manufactured by BASF Japan K.K
*8 Firstgen blue 5380; DIC corporation
*9 Plast Yellow 8025; from Nippon chemical industries Ltd
*10 Balck-T/SD-TT 2259; RESINO COLOR INDUSTRY CO., LTD. PREPARATION
*11 BYK-180；BYManufactured by K Japan Co., Ltd
*12 Silicon KS-66; Shin-Etsu Silicone products
*13 JMT-784; DKSH Japan K.K.
*14 Omirad 379; manufactured by IGM Resins
*15 Exolit (registered trademark) OP 935; manufactured by Clariant corporation
*16 Erosil # R974; manufactured by Dongxi Kabushiki Kaisha
*17 Melamine; nissan chemical Co., Ltd
*18 UCN-5050D Clear; dari refining chemical industry Co., Ltd
*19 Dawanol DPM; manufactured by Dow Chemical Company
*20 EPOLEAD PB 3600; manufactured by Daicel corporation
*21 NK Ester APG-700; manufactured by Xinzhongcun chemical industry Co., Ltd
*22 BPE-900; manufactured by Xinzhongcun chemical industry Co., Ltd
*23 HP-7200L; DIC corporation
*24 jER YX-4000; manufactured by Mitsubishi Chemical Corporation
*25 TEPIC (registered trademark) -VL; nissan chemical Co Ltd
*26 TEPIC (registered trademark) -HP; nissan chemical Co., Ltd
Cured coating films (solder resist layers) were prepared from the curable compositions of examples 1 to 7 and comparative examples 1 to 2 obtained in table 1, and the cured coating films were tested for flux resistance, developability, and bendability as described below.
< test example 1. evaluation of flux resistance >
Examples 1 to 7 and comparative examples were each applied to a copper foil plate having a thickness of 1.6mm pretreated (0.20 vol% hydrogen peroxide sulfate) by screen printing over the entire surface thereof1 to 2, wherein the film thickness after drying is 20 + -5 μm. Then, the substrate was dried at 80 ℃ for 30 minutes in a hot air circulating drying furnace, and then exposed to light (150 mJ/cm) in a 5X 5 grid pattern of 1mm each 2 ) Using 1 wt% Na 2 CO 3 The above alkaline developing solution (30 ℃) was used for development for 60 seconds, and then thermally cured at a temperature of 150 ℃ or higher for 60 minutes to obtain cured coating films of examples 1 to 7 and comparative examples 1 to 2, respectively.
Then, the cured coating films were each coated with flux (SF-270; manufactured by Sanwa Kagaku Corp.), mounted with a dummy wafer (dummy wafer), subjected to a heat treatment in a 230 ℃ air-conveying belt furnace at the top for 5 minutes at a speed of 1.5 m/min, and then peeled off with a cellophane tape of 1.18N/cm or more as defined in JIS Z1522: 2009 to evaluate the degree of peeling of the cured coating films. The evaluation was as follows.
Has a peeling area of 10% or less
The area peeled off after the peeling test exceeded 10% and was 50% or less
The area of the peel after the peel test is over 50% and 100%)
< test example 2 developability >
The curable compositions of examples 1 to 7 and comparative examples 1 to 2 were applied to a copper foil plate having a thickness of 1.6mm pretreated (0.20 vol% hydrogen peroxide sulfate) by screen printing so that the thickness after drying became 20. + -.5. mu.m, and then dried in a hot air circulation type drying oven at 80 ℃ for 30 minutes to obtain dry coating films of examples 1 to 7 and comparative examples 1 to 2, respectively. Then used in a spray type under a pressure of 0.1MPa to make the dried coating film in 1 wt% Na 2 CO 3 The developing was carried out in a solution (30 ℃ C.), and the developing time (dissolution time) was measured to evaluate the developability. The evaluation was as follows.
Developing time less than 20 seconds-
Development time 20 seconds or more to 25 seconds or less
Development time over 25 seconds
< test example 3. bendability >
The curable compositions of examples 1 to 7 and comparative examples 1 to 2 were applied to polyimide films 25 μm thick over the entire surfaces thereof by screen printing so that the thickness after drying was 20. + -.5 μm. Then, the resultant was dried at 80 ℃ for 30 minutes in a hot air circulation type drying furnace, and then exposed to light (150 mJ/cm) 2 ) Using 1 wt% Na 2 CO 3 The cured coating films of examples 1 to 7 and comparative examples 1 to 2 were obtained by carrying out development for 60 seconds in an alkali developing solution (30 ℃) and then heat curing at a temperature of 150 ℃ or higher for 60 minutes.
Then, the cured coating film was bent at 180 degrees and a 500g weight was applied for 10 seconds, and the number of times of bending until cracks were generated on the surface of the cured coating film was measured. The evaluation was as follows.
Bent more than 5 times-
Bending more than 2 times
Bending less than 2 times
The test results of the above test examples 1 to 3 are shown in table 2 below.
[ Table 2]
TABLE 2 test results
Figure BDA0003734590670000241

Claims (10)

1. A curable composition comprising:
(A) an alkali-soluble resin having at least any one structure of a bisphenol a structure, a bisphenol F structure, and a urethane structure;
(B) a photopolymerization initiator; and the combination of (a) and (b),
(C) an epoxy resin having an isocyanurate structure, wherein,
the epoxy resin having an isocyanurate structure (C) has a structure in which a nitrogen atom and an epoxy group in the isocyanurate structure are bonded to each other by an alkylene chain having 2 or more carbon atoms.
2. The curable composition according to claim 1, further comprising a powder or a crystalline epoxy resin.
3. The curable composition according to claim 2, wherein the powder or the crystalline epoxy resin is an epoxy resin having a biphenyl structure.
4. The curable composition according to any one of claims 1 to 3, further comprising an epoxy resin having a dicyclopentadiene structure.
5. The curable composition according to claim 4, wherein the mass ratio of the epoxy resin having an isocyanurate structure (C) to the epoxy resin having a dicyclopentadiene structure (C) to the epoxy resin having a powder or crystalline epoxy resin is 1: 2-6: 1 to 3.
6. The curable composition according to any one of claims 1 to 5, further comprising urethane beads and/or epoxidized polybutadiene.
7. The curable composition according to any one of claims 1 to 6, further comprising a cellulose resin.
8. A dry film comprising a resin layer obtained from the curable composition according to any one of claims 1 to 7.
9. A cured product obtained by curing the curable composition according to any one of claims 1 to 7 or the resin layer of the dry film according to claim 8.
10. An electronic component comprising the cured product according to claim 9.
CN202180008557.8A 2020-02-03 2021-01-08 Curable composition, dry film thereof, and cured product thereof Pending CN114945611A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020016202 2020-02-03
JP2020-016202 2020-02-03
PCT/JP2021/000504 WO2021157282A1 (en) 2020-02-03 2021-01-08 Curable composition, and dry film and cured object obtained therefrom

Publications (1)

Publication Number Publication Date
CN114945611A true CN114945611A (en) 2022-08-26

Family

ID=77199605

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180008557.8A Pending CN114945611A (en) 2020-02-03 2021-01-08 Curable composition, dry film thereof, and cured product thereof

Country Status (5)

Country Link
JP (1) JPWO2021157282A1 (en)
KR (1) KR20220137873A (en)
CN (1) CN114945611A (en)
TW (1) TW202146501A (en)
WO (1) WO2021157282A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023139682A1 (en) * 2022-01-19 2023-07-27 株式会社レゾナック Photosensitive resin composition, photosensitive element, printed wiring board, and method for manufacturing printed wiring board

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1165117A (en) 1997-08-27 1999-03-05 Tamura Kaken Kk Photosensitive resin composition and solder resist ink using that
JP5673963B2 (en) * 2010-01-26 2015-02-18 日産化学工業株式会社 Positive resist composition and method for producing microlens
EP2530098A4 (en) * 2010-01-26 2015-09-09 Nissan Chemical Ind Ltd Long-chain alkylene-containing curable epoxy resin composition
JP6538429B2 (en) * 2014-10-17 2019-07-03 太陽インキ製造株式会社 Dry film, cured product and printed wiring board
WO2019065902A1 (en) * 2017-09-29 2019-04-04 東レ株式会社 Photosensitive resin composition, cured film, element having cured film, organic el display, and method for manufacturing organic el display
WO2020066049A1 (en) * 2018-09-28 2020-04-02 太陽インキ製造株式会社 Curable resin composition, dry film, cured product, laminated structure, and electronic component

Also Published As

Publication number Publication date
KR20220137873A (en) 2022-10-12
JPWO2021157282A1 (en) 2021-08-12
WO2021157282A1 (en) 2021-08-12
TW202146501A (en) 2021-12-16

Similar Documents

Publication Publication Date Title
CN106662813B (en) Curable resin composition, dry film, cured product, and printed wiring board
KR102369508B1 (en) Curable resin composition, dry film, cured product and printed wiring board
KR20120060938A (en) Photo-sensitive resin composition, dry film solder resist, and circuit board
WO2018143220A1 (en) Photocurable resin composition, dry film, cured product, and printed wiring board
JP2019179230A (en) Curable resin composition, dry film, cured product and printed wiring board
JP2019174787A (en) Photosensitive resin composition, two-liquid type photosensitive resin composition, dry film and printed wiring board
JP2018173609A (en) Curable resin composition, dry film, cured product, and printed wiring board
WO2023190456A1 (en) Cured product, photosensitive resin composition, dry film, and printed wiring board
CN114945611A (en) Curable composition, dry film thereof, and cured product thereof
JP2019179232A (en) Dry film, cured product and printed wiring board
CN111708251B (en) Curable resin composition, dry film, cured product, and electronic component
JP7298079B2 (en) Curable resin composition, dry film, cured product and electronic parts
JP6724097B2 (en) Curable resin composition, dry film, cured product, printed wiring board and electronic component
CN113448166A (en) Curable resin composition, dry film, cured product, and electronic component
CN113631603A (en) Curable resin composition, dry film, cured product, and electronic component
JP7339103B2 (en) Curable resin composition, dry film, cured product, and electronic component
JP7445095B2 (en) Photosensitive resin compositions, dry films, cured products, and printed wiring boards
WO2023190393A1 (en) Cured product and printed wiring board
WO2023190455A1 (en) Photosensitive resin composition, cured product, printed circuit board, and method for producing printed circuit board
JP2022155116A (en) Photosensitive resin composition, dry film, hardened material, and electronic component
WO2024075717A1 (en) Curable resin composition, dry film, cured product, and printed wiring board
WO2022050372A1 (en) Photocurable thermosetting resin composition, dry film, cured product, and electronic component comprising cured product
JP2024065105A (en) CURABLE RESIN COMPOSITION, METHOD FOR PRODUCING CURED PRODUCT OF THE CURABLE RESIN COMPOSITION, AND METHOD FOR PRODUCING PRINTED WIRING BOARD COMPRISING THE CURED PRODUCT
WO2024075714A1 (en) Photosensitive resin composition, dry film, cured product and printed wiring board
US20220325128A1 (en) Two-component type curable resin composition, product, dry film, cured product, and printed wiring board

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20230922

Address after: Saitama Prefecture, Japan

Applicant after: TAIYO HOLDINGS Co.,Ltd.

Address before: Saitama Prefecture, Japan

Applicant before: TAIYO INK MFG. Co.,Ltd.

TA01 Transfer of patent application right