WO2011030580A1 - Photosensitive composition and printed wiring board - Google Patents

Photosensitive composition and printed wiring board Download PDF

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Publication number
WO2011030580A1
WO2011030580A1 PCT/JP2010/056183 JP2010056183W WO2011030580A1 WO 2011030580 A1 WO2011030580 A1 WO 2011030580A1 JP 2010056183 W JP2010056183 W JP 2010056183W WO 2011030580 A1 WO2011030580 A1 WO 2011030580A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive composition
aromatic ring
titanium oxide
carboxyl group
compound
Prior art date
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PCT/JP2010/056183
Other languages
French (fr)
Japanese (ja)
Inventor
秀 中村
貴史 西村
崇至 鹿毛
貴志 渡邉
駿夫 ▲高▼橋
Original Assignee
積水化学工業株式会社
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Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201080038203XA priority Critical patent/CN102483571B/en
Priority to KR1020127004221A priority patent/KR101317963B1/en
Priority to JP2010513521A priority patent/JP4897922B2/en
Priority to KR1020127004277A priority patent/KR101307144B1/en
Publication of WO2011030580A1 publication Critical patent/WO2011030580A1/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10106—Light emitting diode [LED]
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
    • H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics

Definitions

  • the present invention relates to a photosensitive composition suitably used for forming a resist film such as a solder resist film formed on a substrate or a resist film reflecting light formed on a substrate on which a light emitting diode chip is mounted. And a printed wiring board using the photosensitive composition.
  • a light emitting diode (hereinafter abbreviated as LED) chip is mounted on the upper surface of a printed wiring board.
  • a white solder resist film may be formed on the upper surface of the printed wiring board in order to use light that has reached the upper surface side of the printed wiring board among the light emitted from the LEDs.
  • not only light directly irradiated from the surface of the LED chip to the opposite side of the printed wiring board but also reflected light that reaches the upper surface side of the printed wiring board and is reflected by the white solder resist film can be used. . Therefore, the utilization efficiency of the light generated from the LED can be increased.
  • Patent Document 1 contains an alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholization reaction between an epoxy resin and a hydrolyzable alkoxysilane.
  • a resist composition further containing an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and a cured adhesion-imparting agent is disclosed.
  • Patent Document 2 discloses a white solder resist composition containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, a rutile-type titanium oxide, and a diluent. It is disclosed.
  • the resist film When a resist film is formed using the resist composition described in Patent Documents 1 and 2, the resist film turns yellow when exposed to a high temperature of about 200 ° C. or higher as in solder reflow (hereinafter, (Abbreviated as yellowing). Furthermore, when the resist film is exposed to high temperatures, cracks may occur.
  • An object of the present invention is to provide a photosensitive composition capable of forming a resist film having excellent heat cracking resistance, and a printed wiring board using the photosensitive composition.
  • a photosensitive composition comprising a carboxyl group-containing resin having an aromatic ring, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator.
  • the carboxyl group-containing resin having an aromatic ring has an unsaturated double bond.
  • the carboxyl group-containing resin having an aromatic ring is a resin obtained by reacting an epoxy compound having an aromatic ring with a polybasic acid compound, or at least one epoxy compound having an aromatic ring and an unsaturated double bond. A resin obtained by further reacting a polybasic acid compound after reacting with the carboxyl group-containing compound is preferred.
  • the carboxyl group-containing resin having an aromatic ring includes at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. It is desirable to have one structural unit.
  • the compound having a cyclic ether skeleton preferably has an aromatic ring.
  • the titanium oxide is preferably rutile type titanium oxide. It is preferable that the said titanium oxide contains the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound.
  • the photosensitive composition according to the present invention preferably further contains an antioxidant.
  • the antioxidant is preferably a phenolic antioxidant.
  • the photosensitive composition does not contain a phenolic antioxidant or further contains a phenolic antioxidant and has a carboxyl group-containing resin having the aromatic ring.
  • the number of moles of the first structural unit of the group-containing resin is V
  • the second structural unit of the carboxyl group-containing resin having the aromatic ring The number of moles of the rutile titanium oxide surface treated with the silicon oxide or silicone compound is X1, and the number of moles of the titanium oxide that is not the rutile titanium oxide surface treated with the silicon oxide or silicone compound is W1.
  • a two-liquid mixed type having a first liquid and a second liquid and used by mixing the first and second liquids.
  • the carboxyl group-containing resin having an aromatic ring, the titanium oxide, the compound having the cyclic ether skeleton, and the photopolymerization initiator are the first liquid and the second liquid, respectively.
  • the mixture of the first and second liquids has a carboxyl group-containing resin having the aromatic ring, the titanium oxide, and the cyclic ether skeleton. A compound and the photopolymerization initiator.
  • the first liquid includes at least a carboxyl group-containing resin having an aromatic ring
  • the second liquid includes at least a compound having the cyclic ether skeleton.
  • a printed wiring board according to the present invention includes a printed wiring board main body having a circuit on the surface, and a resist film laminated on the surface of the printed wiring board main body on which the circuit is provided. It is formed using the photosensitive composition comprised according to this.
  • the photosensitive composition according to the present invention includes a carboxyl group-containing resin having an aromatic ring, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator. Obtainable.
  • the photosensitive composition according to the present invention contains an antioxidant, a resist film excellent in heat-resistant yellowing can be obtained.
  • FIG. 1 is a partially cutaway front sectional view showing an example of an LED device having a resist film using the photosensitive composition according to the present invention.
  • the photosensitive composition according to the present invention comprises (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, (C) a compound having a cyclic ether skeleton, and (D) a photopolymerization initiator. Including.
  • the carboxyl group-containing resin having an aromatic ring (A) contained in the photosensitive composition according to the present invention is not particularly limited as long as it has an aromatic ring and a carboxyl group.
  • As for carboxyl group-containing resin which has an aromatic ring only 1 type may be used and 2 or more types may be used together.
  • the carboxyl group-containing resin having an aromatic ring is preferably the following carboxyl group-containing resins (a) to (e).
  • a compound having a benzene ring, a benzene ring having a substituent, a polycyclic aromatic ring or a heteroaromatic ring is used.
  • the substituent substituted on the benzene ring include alkyl groups, hydroxyl groups, and halogen atoms such as bromine and chlorine.
  • Examples of the polyaromatic ring include a naphthalene ring and an anthracene ring.
  • the heteroaromatic ring includes N, S, O and the like. Examples of the heteroaromatic ring include a pyridine ring, a pyrrole ring, an imidazole ring, and a thiophene ring.
  • the secondary hydroxyl group of the resulting reaction product is saturated or unsaturated polybasic.
  • Carboxyl group-containing resin obtained by reacting acid anhydride (d) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is added to one molecule.
  • Hydroxyl and carboxyl group-containing resins obtained by reacting compounds each having one epoxy group and a polymerizable unsaturated double bond (e) Epoxy compounds having aromatic rings and saturated polybasic acid anhydrides and unsaturated compounds A resin obtained by reacting a polybasic acid compound such as a polybasic acid anhydride, or an epoxy compound having an aromatic ring and a carboxyl group-containing compound having at least one unsaturated double bond, and then saturated. Resins obtained by further reacting polybasic acid compounds such as polybasic acid anhydrides and unsaturated polybasic acid anhydrides
  • the carboxyl group-containing resin having an aromatic ring is a resin obtained by reacting an epoxy compound having an aromatic ring with a polybasic acid compound, or a carboxyl having at least one unsaturated double bond with an epoxy compound having an aromatic ring.
  • a resin obtained by further reacting a polybasic acid compound after reacting with the group-containing compound is preferred. In this case, the heat crack resistance of the resist film can be further enhanced.
  • Examples of the epoxy compound having an aromatic ring include bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, biphenyl type, naphthalene type, trisphenolmethane type, dicyclopentadiene / phenylene type, phenol / biphenylene type, phenoxy Type, glycidylamine type, bisphenol S type epoxy compounds, glycidyl esterified products of basic acids such as diglycidyl phthalate and glycidyl p-hydroxybenzoate, and triglycidyl isocyanurate.
  • the acid value of the carboxyl group-containing resin having an aromatic ring is preferably in the range of 50 to 200 mgKOH / g.
  • the acid value is 50 mgKOH / g or more, unexposed portions can be easily removed even with a weak alkaline aqueous solution during development.
  • the acid value is 200 mgKOH / g or less, the water resistance and electrical properties of the cured coating are further enhanced.
  • the weight average molecular weight of the (A) carboxyl group-containing resin having an aromatic ring is preferably in the range of 5,000 to 100,000. When the weight average molecular weight is 5,000 or more, the drying property when touched with a finger is further improved. Further, when the weight average molecular weight is 100,000 or less, the developability after exposure of the photosensitive composition and the storage stability of the photosensitive composition are further enhanced.
  • the (A) carboxyl-containing group resin includes at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. It is desirable to have one structural unit.
  • examples of the aromatic ring in the first structural unit and the second structural unit include a benzene ring, a benzene ring having a substituent, a polycyclic aromatic ring, and a heteroaromatic ring.
  • substituent substituted on the benzene ring include alkyl groups, hydroxyl groups, and halogen atoms such as bromine and chlorine.
  • polyaromatic ring include a naphthalene ring and an anthracene ring.
  • the heteroaromatic ring includes N, S, O and the like.
  • Examples of the heteroaromatic ring include a pyridine ring, a pyrrole ring, an imidazole ring, and a thiophene ring.
  • the carboxyl group-containing resin having the first structural unit examples include an aromatic epoxy resin having a first structural unit such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, or a bisphenol F epoxy resin, A carboxyl group-containing resin obtained by reacting a polybasic acid compound such as phthalic acid or phthalic anhydride, or the above-mentioned aromatic epoxy resin and a basic acid compound having an unsaturated double bond such as (meth) acrylic acid
  • the resin include an unsaturated double bond and a carboxyl group obtained by further reacting with a polybasic acid compound such as phthalic acid or phthalic anhydride after the reaction.
  • the carboxyl group-containing resin having the second structural unit examples include an aromatic epoxy resin such as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, and a phthalate.
  • the resin include an unsaturated double bond and a carboxyl group obtained by further reacting with a polybasic acid compound such as phthalic acid or phthalic anhydride after the reaction.
  • the carboxyl group-containing resin has at least one of the first structural unit and the second structural unit, the heat yellowing resistance and crack resistance of the resist film are further enhanced. be able to.
  • the two aromatic rings in the first structural unit are preferably a benzene ring or a benzene ring having a substituent.
  • the first structural unit is preferably a structural unit represented by the following formula (11).
  • the covalent bond shown in the following formula (11) may be bonded at any position with respect to the phenylene group.
  • the phenylene group may be substituted.
  • the aromatic ring in the second structural unit is preferably a benzene ring or a benzene ring having a substituent.
  • the second structural unit is preferably a structural unit represented by the following formula (12).
  • the covalent bond shown in the following formula (12) may be bonded at any position with respect to the phenylene group.
  • the phenylene group may be substituted.
  • the photosensitive composition according to the present invention does not contain a phenolic antioxidant or further contains a phenolic antioxidant, and the carboxyl group-containing resin having an aromatic ring has two aromatic rings via a methylene group. And at least one structural unit of the second structural unit in which the oxymethylene group and the aromatic ring are ether-bonded, and the titanium oxide is formed by a silicon oxide or a silicone compound.
  • the first structural unit of the carboxyl group-containing resin not containing surface-treated rutile-type titanium oxide or containing rutile-type titanium oxide surface-treated with the silicon oxide or silicone compound and having the aromatic ring The number of moles is V, the number of moles of the second structural unit of the carboxyl group-containing resin having an aromatic ring is W, and the silicon oxide or X1 is the number of moles of rutile titanium oxide surface-treated with a silicone compound, X2 is the number of moles of titanium oxide that is not a rutile titanium oxide surface-treated with the above silicon oxide or silicone compound, and the above phenolic oxidation.
  • the photosensitive composition according to the present invention preferably satisfies the following formula (1).
  • the heat yellowing resistance of the resist film can be further enhanced and the heat cracking resistance can be enhanced.
  • the (B) titanium oxide contained in the photosensitive composition according to the present invention is not particularly limited.
  • the titanium oxide is preferably rutile titanium oxide or anatase titanium oxide.
  • rutile type titanium oxide By using rutile type titanium oxide, a more excellent resist film can be formed by heat-resistant yellowing.
  • the anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. For this reason, the use of anatase-type titanium oxide can improve the processability of the resist film.
  • the titanium oxide preferably contains rutile titanium oxide surface-treated with silicon oxide or a silicone compound.
  • the content of the rutile titanium oxide surface-treated with the silicon oxide or the silicone compound is desirably 10% by weight or more, and more desirably 30% by weight or more.
  • the titanium oxide is more preferably rutile titanium oxide surface-treated with the silicon oxide or silicone compound. In these cases, the heat-resistant yellowing of the resist film can be further enhanced.
  • Examples of the rutile type titanium oxide surface-treated with silicon oxide or silicone compound include, for example, product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is rutile chlorine method titanium oxide, and manufactured by Ishihara Sangyo Co., Ltd., which is rutile sulfuric acid method titanium oxide. Product number: R-550 and the like.
  • the content of (B) titanium oxide is preferably 3% by weight or more and 80% by weight or less.
  • the minimum with preferable content of titanium oxide is 10 weight%, and a preferable upper limit is 75 weight%.
  • the content of titanium oxide is within the above range, yellowing hardly occurs when the resist film is exposed to a high temperature. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.
  • the compound (C) having a cyclic ether skeleton contained in the photosensitive composition according to the present invention is not particularly limited as long as it has a cyclic ether skeleton.
  • Examples of compounds having a cyclic ether skeleton include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, and tetraglycidyl.
  • heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, and tetraglycidyl.
  • Xylenoylethane resin bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin Bisphenol A novolac epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol Click type epoxy resin, and silicone-modified epoxy resins, and ⁇ - caprolactone modified epoxy resin.
  • the compound having a cyclic ether skeleton preferably has an aromatic ring.
  • the heat crack resistance of the resist film can be further enhanced.
  • Examples of the epoxy compound having an aromatic ring include bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, biphenyl type, naphthalene type, trisphenolmethane type, dicyclopentadiene / phenylene type, phenol / biphenylene type, phenoxy Type, glycidylamine type, bisphenol S type epoxy compounds, glycidyl esterified products of basic acids such as diglycidyl phthalate and glycidyl p-hydroxybenzoate, and triglycidyl isocyanurate.
  • the preferable lower limit of the content of the compound (C) having a cyclic ether skeleton is 0.1 parts by weight, and the more preferable lower limit is 1 part by weight, with respect to 100 parts by weight of the carboxyl group-containing resin having an aromatic ring. Is 50 parts by weight, and a more preferred upper limit is 30 parts by weight.
  • (D) Photopolymerization initiator Since the photosensitive composition which concerns on this invention contains the photoinitiator (D), it has photosensitivity.
  • the photopolymerization initiator is not particularly limited.
  • acylphosphine oxide for example, acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, benzoate, Examples thereof include acridine, phenazine, titanocene, ⁇ -aminoalkylphenone, oxime, and derivatives thereof.
  • the preferable lower limit of the content of the photopolymerization initiator (D) is 0.1 parts by weight, the more preferable lower limit is 1 part by weight, and the preferable upper limit is 30 parts per 100 parts by weight of the carboxyl group-containing resin having an aromatic ring. Part by weight, more preferred upper limit is 15 parts by weight.
  • the photosensitive composition according to the present invention preferably contains (E) a diluent.
  • a diluent By using a diluent, the photosensitive composition can be easily applied.
  • the diluent is used to adjust the viscosity of the photosensitive composition to improve workability, to increase the crosslink density, and to improve adhesion.
  • a diluent reactive diluents, such as a photopolymerizable monomer, and a well-known usual solvent can be used. Examples of the solvent include organic solvents and water.
  • Examples of the photopolymerizable monomer include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate, and hydroxy such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate
  • hydroxy such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • (meth) acrylates having a hydrophilic group are preferred.
  • polyfunctional (meth) acrylates are preferable.
  • a preferable upper limit of the content of the photopolymerizable monomer is 20% by weight, and a more preferable upper limit is 10% by weight.
  • organic solvent examples include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl.
  • Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate , Esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, and petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha. As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.
  • the content of the diluent is not particularly limited. In consideration of the coating property of the photosensitive composition, the (E) diluent is used in an appropriate content.
  • the photosensitive composition according to the present invention preferably contains (F) an antioxidant.
  • antioxidant As for antioxidant, only 1 type may be used and 2 or more types may be used together.
  • the antioxidant preferably has a Lewis basic moiety.
  • the antioxidant is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Preferably there is.
  • the (F) antioxidant is preferably a phenolic antioxidant.
  • IRGANOX 1010 Commercially available products of the above-mentioned phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295 (all of which are manufactured by Ciba Japan), Adeka Stub AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sum riser GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14
  • Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine.
  • Commercially available products of the above-mentioned phosphoric antioxidants include Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, 1500, Adeastab C, Adeastab 135A, Adeastab 3010, Adeastab TPP (all made by ADEKA), Sandstub P-EPQ, Hostanox PAR24 (all made by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, JPH-3800 (all of these Kitakagaku Kogyo Co., Ltd.), and the like.
  • amine antioxidant examples include triethylamine, dicyandiamide, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine, 2,4- Examples thereof include diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.
  • the preferred lower limit of the content of (F) antioxidant is 0.1 parts by weight, the more preferred lower limit is 5 parts by weight, and the preferred upper limit is 30 parts by weight. Parts, more preferred upper limit is 15 parts by weight.
  • (F) When the content of the antioxidant satisfies the above preferable lower limit and upper limit, a more excellent resist film can be formed by heat-resistant yellowing.
  • the photosensitive composition according to the present invention includes a colorant, a filler, an antifoaming agent, a curing agent, a curing accelerator, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface. It may contain a modifier, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent or a phosphor.
  • the photosensitive composition according to the present invention may be a one-component type photosensitive composition. Furthermore, the photosensitive composition according to the present invention may be a film-like photosensitive composition. A known method can be used as a method for forming the photosensitive composition into a film. The film includes a sheet.
  • the photosensitive composition according to the present invention has a first liquid and a second liquid, and the two-liquid mixed photosensitive composition used by mixing the first and second liquids. It may be.
  • the two-component mixed photosensitive composition the progress of polymerization or curing reaction before use can be suppressed. For this reason, the pot life of each of the two liquids can be improved.
  • a two-component mixed photosensitive composition (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, (C) a compound having a cyclic ether skeleton, and (D) photopolymerization.
  • Each initiator is included in at least one of the first liquid and the second liquid.
  • the mixture in which the first and second liquids are mixed is a photosensitive composition having (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, and (C) a cyclic ether skeleton. A compound and (D) a photopolymerization initiator.
  • the first liquid includes at least (A) a carboxyl group-containing resin having an aromatic ring
  • the second liquid includes (C) a cyclic ether skeleton. It is preferable to include at least a compound having The first liquid does not include (C) a compound having a cyclic ether skeleton, includes (A) a carboxyl group-containing resin having an aromatic ring, and the second liquid has (A) an aromatic ring. More preferably, it does not include a carboxyl group-containing resin and includes (C) a compound having a cyclic ether skeleton. That is, it is more preferable that (A) the carboxyl group-containing resin having an aromatic ring and (C) the compound having a cyclic ether skeleton are not contained in the same liquid but contained in different liquids.
  • the photosensitive composition according to the present invention can be prepared, for example, by stirring and mixing the ingredients and then uniformly mixing with three rolls.
  • Examples of the light source used for curing the photosensitive composition include an irradiation device that emits active energy rays such as ultraviolet rays or visible rays.
  • Examples of the light source include an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources are appropriately selected according to the photosensitive wavelength of the constituent components of the photosensitive composition.
  • the irradiation energy of light is appropriately selected depending on the desired film thickness or the constituent components of the photosensitive composition.
  • the irradiation energy of light is generally in the range of 10 to 3000 mJ / cm 2 .
  • the photosensitive composition concerning this invention is used suitably for the use which forms the resist film of a printed wiring board, and is used suitably by the use which forms a soldering resist film.
  • the photosensitive composition according to the present invention is preferably a resist composition, and more preferably a solder resist composition.
  • the printed wiring board according to the present invention includes a printed wiring board body having a circuit on the surface, and a resist film laminated on the surface of the printed wiring board body on which the circuit is provided.
  • the resist film is formed of the photosensitive composition according to the present invention.
  • the photosensitive composition according to the present invention is suitably used for forming a resist film in an LED device in which an LED chip is mounted on a substrate, and is preferably used for forming a solder resist film.
  • FIG. 1 is a partially cutaway front sectional view schematically showing an example of an LED device including a solder resist film formed using the photosensitive composition according to the present invention.
  • a solder resist film 3 is formed on a substrate 2.
  • An LED chip 7 is mounted on the solder resist film 3.
  • the substrate 2 is a laminated substrate having a glass layer 5 and a resin layer 6.
  • substrate 2 is not specifically limited, Not only the laminated board which consists of resin and another material, You may be formed with other laminated boards, such as a ceramic multilayer board
  • the solder resist film 3 is formed by coating the photosensitive composition of the present invention on the substrate 2, exposing and developing. More specifically, after forming the electrodes 4 a and 4 b, the photosensitive composition is applied to the entire region on the substrate 2. Next, the photosensitive composition is selectively exposed from above using a mask in which the portions where the electrodes 4a and 4b are located are light shielding portions. The photosensitive composition is cured in a region irradiated with light by exposure. Curing of the photosensitive composition does not proceed in the region covered with the light shielding part. Therefore, the unexposed photosensitive composition portion is removed using a solvent that dissolves the uncured photosensitive composition. In this way, the solder resist film 3 having the openings 3a and 3b shown in FIG. 1 can be obtained. The electrodes 4a and 4b are exposed in the openings 3a and 3b, respectively.
  • the LED chip 7 having the terminals 8a and 8b on the lower surface 7a is mounted on the solder resist film 3, and the terminals 8a and 8b and the electrodes 4a and 4b are joined by solders 9a and 9b, respectively. In this way, the LED device 1 is obtained.
  • the LED device 1 when the LED chip 7 is driven, light is emitted as indicated by a broken line. In this case, not only the light irradiated from the LED chip 7 to the side opposite to the upper surface 2a of the substrate 2, that is, the light irradiated on the upper side, but also the light reaching the solder resist film 3 is reflected as indicated by an arrow A.
  • the solder resist film 3 is white and reflects the light with high efficiency. Therefore, since the reflected light indicated by the arrow A is also used, the light use efficiency of the LED chip 7 can be increased.
  • a carboxyl group-containing resin having an aromatic ring (A1) to (A7) and a carboxyl group-containing resin having no aromatic ring were prepared.
  • the carboxyl group-containing resins obtained in Synthesis Examples 1, 6, and 7 correspond to the carboxyl group-containing resins having the first and second structural units.
  • the carboxyl group-containing resins obtained in Synthesis Examples 5 and 8 correspond to the carboxyl group-containing resin having the second structural unit.
  • Glycidyl acrylate was added in such an amount that the molar ratio of the total amount of all the monomer units of the obtained resin was 10 and then heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight of a carboxyl group-containing resin having an aromatic ring with a solid content acid value of 60 mgKOH / g.
  • this solution is referred to as (A2) a carboxyl group-containing resin having an aromatic ring.
  • Titanium oxide Details of titanium oxide used in the following examples and comparative examples are as follows. Rutile type titanium oxide (1): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-97. Rutile-type titanium oxide produced by the chlorine method. Rutile type titanium oxide (2): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-50. Rutile-type titanium oxide produced by the chlorine method. Rutile type titanium oxide (3): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-90. It is treated with rutile titanium oxide and silica produced by the chlorine method.
  • Rutile sulfuric acid method titanium oxide (1) Rutile titanium oxide produced by the sulfuric acid method, manufactured by Ishihara Sangyo Co., Ltd., product number: R-630.
  • Rutile sulfuric acid method titanium oxide (2) Rutile type titanium oxide produced by the sulfuric acid method, manufactured by Ishihara Sangyo Co., Ltd., product number: R-550. Treated with silica. Anatase type titanium oxide: manufactured by Ishihara Sangyo Co., Ltd., product number: A-220.
  • Example 1 25 parts by weight of the carboxyl group-containing resin (A1) having an aromatic ring obtained in Synthesis Example 1, 40 parts by weight of a rutile type chlorine method titanium oxide (“CR-97” manufactured by Ishihara Sangyo Co., Ltd.), and a bisphenol A type epoxy resin (“JER828” manufactured by Japan Epoxy Resin Co., Ltd.) 8 parts by weight, 2 parts by weight of photopolymerization initiator (photo radical generator, "TPO” manufactured by BASF Japan), and phenolic antioxidant (“IRGANOX” manufactured by Ciba Japan) 1010 ”) 0.5 parts by weight, 5 parts by weight of dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel Cytec) as a diluent, and 20 parts by weight of ethyl carbitol acetate (manufactured by Daicel Chemical Industries), After mixing for 3 minutes with a mixer (Nertaro SP-500, manufactured by Shinky Corp.), the mixture was mixed with
  • Examples 2 to 23 and Comparative Examples 1 to 5 A photosensitive composition was obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Tables 3 to 6 below.
  • the resist material layer was dipped in a 1% by weight aqueous solution of sodium carbonate and developed to form a resist film on the substrate. Thereafter, the resist film was post-cured by heating in an oven at 150 ° C. for 1 hour to obtain a resist film as a measurement sample. The thickness of the obtained resist film was 20 ⁇ m.
  • Example 24 The materials shown in Table 7 below are blended in the amounts shown in Table 7 below, mixed for 3 minutes with a mixer (Nertaro SP-500, manufactured by Shinky Corp.), then mixed with 3 rolls, and the mixture Got. Thereafter, the obtained mixture was degassed for 3 minutes using SP-500 to obtain a first liquid.
  • a mixer Netaro SP-500, manufactured by Shinky Corp.
  • Examples 25 to 35 Two-component mixed type photosensitivity in the same manner as in Example 24, except that the types and amounts of materials used in the first and second liquids were changed as shown in Tables 7 and 8 below. A composition was obtained.

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Abstract

Disclosed are: a photosensitive composition which enables the formation of a resist film having excellent heat cracking resistance; and a printed wiring board produced using the photosensitive composition. The photosensitive composition comprises a resin having an aromatic ring and containing a carboxyl group, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator. The printed wiring board comprises a printed wiring board main body having a circuit formed on the surface thereof, and a resist film (3) laminated on the surface of the printed wiring board main body on which the circuit has been provided. The resist film (3) is formed using the photosensitive composition.

Description

感光性組成物及びプリント配線板Photosensitive composition and printed wiring board
　本発明は、基板上に形成させるソルダーレジスト膜や、発光ダイオードチップが搭載される基板上に形成される光を反射させるレジスト膜などのレジスト膜を形成するために好適に用いられる感光性組成物、並びに該感光性組成物を用いたプリント配線板に関する。 The present invention relates to a photosensitive composition suitably used for forming a resist film such as a solder resist film formed on a substrate or a resist film reflecting light formed on a substrate on which a light emitting diode chip is mounted. And a printed wiring board using the photosensitive composition.
　様々な電子機器用途において、プリント配線板の上面に発光ダイオード（以下、ＬＥＤと略す）チップが搭載されている。ＬＥＤから発せられた光の内、上記プリント配線板の上面側に到達した光も利用するために、プリント配線板の上面に白色ソルダーレジスト膜が形成されていることがある。この場合には、ＬＥＤチップの表面からプリント配線板とは反対側に直接照射される光だけでなく、プリント配線板の上面側に到達し、白色ソルダーレジスト膜により反射された反射光も利用できる。従って、ＬＥＤから生じた光の利用効率を高めることができる。 In various electronic equipment applications, a light emitting diode (hereinafter abbreviated as LED) chip is mounted on the upper surface of a printed wiring board. A white solder resist film may be formed on the upper surface of the printed wiring board in order to use light that has reached the upper surface side of the printed wiring board among the light emitted from the LEDs. In this case, not only light directly irradiated from the surface of the LED chip to the opposite side of the printed wiring board but also reflected light that reaches the upper surface side of the printed wiring board and is reflected by the white solder resist film can be used. . Therefore, the utilization efficiency of the light generated from the LED can be increased.
　上記白色ソルダーレジスト膜を形成するための材料の一例として、下記の特許文献１には、エポキシ樹脂と加水分解性アルコキシシランとの脱アルコール反応により得られたアルコキシ基含有シラン変性エポキシ樹脂を含有し、かつ不飽和基含有ポリカルボン酸樹脂と、希釈剤と、光重合開始剤と、硬化密着性付与剤とをさらに含有するレジスト組成物が開示されている。 As an example of a material for forming the white solder resist film, the following Patent Document 1 contains an alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholization reaction between an epoxy resin and a hydrolyzable alkoxysilane. In addition, a resist composition further containing an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and a cured adhesion-imparting agent is disclosed.
　また、下記の特許文献２には、芳香環を有さないカルボキシル基含有樹脂と、光重合開始剤と、エポキシ化合物と、ルチル型酸化チタンと、希釈剤とを含有する白色ソルダーレジスト組成物が開示されている。 Patent Document 2 below discloses a white solder resist composition containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, a rutile-type titanium oxide, and a diluent. It is disclosed.
特開２００７－２４９１４８号公報JP 2007-249148 A 特開２００７－３２２５４６号公報JP 2007-322546 A
　上記特許文献１，２に記載のレジスト組成物を用いてレジスト膜を形成した場合には、はんだリフロー時のような２００℃程度以上の高温に晒されると、レジスト膜が黄色に変色（以下、黄変と略す）することがある。さらに、レジスト膜が高温下に晒されると、クラックが生じることがある。 When a resist film is formed using the resist composition described in Patent Documents 1 and 2, the resist film turns yellow when exposed to a high temperature of about 200 ° C. or higher as in solder reflow (hereinafter, (Abbreviated as yellowing). Furthermore, when the resist film is exposed to high temperatures, cracks may occur.
　本発明の目的は、耐熱クラック性に優れたレジスト膜を形成できる感光性組成物、並びに該感光性組成物を用いたプリント配線板を提供することである。 An object of the present invention is to provide a photosensitive composition capable of forming a resist film having excellent heat cracking resistance, and a printed wiring board using the photosensitive composition.
　本発明の広い局面によれば、芳香環を有するカルボキシル基含有樹脂と、酸化チタンと、環状エーテル骨格を有する化合物と、光重合開始剤とを含む、感光性組成物が提供される。 According to a wide aspect of the present invention, there is provided a photosensitive composition comprising a carboxyl group-containing resin having an aromatic ring, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator.
　上記芳香環を有するカルボキシル基含有樹脂は、不飽和二重結合を有することが好ましい。また、上記芳香環を有するカルボキシル基含有樹脂は、芳香環を有するエポキシ化合物と多塩基酸化合物とを反応させて得られる樹脂、又は芳香環を有するエポキシ化合物と不飽和二重結合を少なくとも１つ有するカルボキシル基含有化合物とを反応させた後、多塩基酸化合物をさらに反応させて得られる樹脂であることが好ましい。 It is preferable that the carboxyl group-containing resin having an aromatic ring has an unsaturated double bond. In addition, the carboxyl group-containing resin having an aromatic ring is a resin obtained by reacting an epoxy compound having an aromatic ring with a polybasic acid compound, or at least one epoxy compound having an aromatic ring and an unsaturated double bond. A resin obtained by further reacting a polybasic acid compound after reacting with the carboxyl group-containing compound is preferred.
　上記芳香環を有するカルボキシル基含有樹脂は、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有することが望ましい。 The carboxyl group-containing resin having an aromatic ring includes at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. It is desirable to have one structural unit.
　上記環状エーテル骨格を有する化合物は、芳香環を有することが好ましい。 The compound having a cyclic ether skeleton preferably has an aromatic ring.
　上記酸化チタンは、ルチル型酸化チタンであることが好ましい。上記酸化チタンは、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含むことが好ましい。 The titanium oxide is preferably rutile type titanium oxide. It is preferable that the said titanium oxide contains the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound.
　本発明に係る感光性組成物は、酸化防止剤をさらに含むことが好ましい。該酸化防止剤はフェノール系酸化防止剤であることが好ましい。 The photosensitive composition according to the present invention preferably further contains an antioxidant. The antioxidant is preferably a phenolic antioxidant.
　本発明に係る感光性組成物のある特定の局面では、感光性組成物が、フェノール系酸化防止剤を含まないか、又はフェノール系酸化防止剤をさらに含み、上記芳香環を有するカルボキシル基含有樹脂が、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有し、上記酸化チタンが、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含まないか、又は該ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含み、上記芳香環を有するカルボキシル基含有樹脂の上記第１の構造単位のモル数をＶとし、上記芳香環を有するカルボキシル基含有樹脂の上記第２の構造単位のモル数をＷとし、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンのモル数をＸ１とし、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンではない酸化チタンのモル数をＸ２とし、かつ上記フェノール系酸化防止剤のフェノール基のモル数をＹとしたときに、下記式（１）を満たす。 In a specific aspect of the photosensitive composition according to the present invention, the photosensitive composition does not contain a phenolic antioxidant or further contains a phenolic antioxidant and has a carboxyl group-containing resin having the aromatic ring. Has at least one structural unit of a first structural unit in which two aromatic rings are bonded via a methylene group and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded, Titanium oxide does not contain rutile-type titanium oxide surface-treated with silicon oxide or silicone compound, or contains rutile-type titanium oxide surface-treated with silicon oxide or silicone compound and has the aromatic ring The number of moles of the first structural unit of the group-containing resin is V, and the second structural unit of the carboxyl group-containing resin having the aromatic ring The number of moles of the rutile titanium oxide surface treated with the silicon oxide or silicone compound is X1, and the number of moles of the titanium oxide that is not the rutile titanium oxide surface treated with the silicon oxide or silicone compound is W1. When the number of moles is X2 and the number of moles of the phenol group of the phenolic antioxidant is Y, the following formula (1) is satisfied.
　０．０６≦（５Ｖ＋３Ｗ）／（３Ｘ１＋Ｘ２＋１００Ｙ）≦０．３５　・・・式（１） 0.06 ≦ (5V + 3W) / (3X1 + X2 + 100Y) ≦ 0.35 Expression (1)
　本発明に係る感光性組成物の他の特定の局面では、第１の液と、第２の液とを有し、該第１，第２の液が混合されて用いられる２液混合型の感光性組成物であり、上記芳香環を有するカルボキシル基含有樹脂と、上記酸化チタンと、上記環状エーテル骨格を有する化合物と、上記光重合開始剤とはそれぞれ、上記第１の液及び上記第２の液の内の少なくとも一方に含まれており、上記第１，第２の液が混合された混合物は、上記芳香環を有するカルボキシル基含有樹脂と、上記酸化チタンと、上記環状エーテル骨格を有する化合物と、上記光重合開始剤とを含む。 In another specific aspect of the photosensitive composition according to the present invention, a two-liquid mixed type having a first liquid and a second liquid and used by mixing the first and second liquids. In the photosensitive composition, the carboxyl group-containing resin having an aromatic ring, the titanium oxide, the compound having the cyclic ether skeleton, and the photopolymerization initiator are the first liquid and the second liquid, respectively. And the mixture of the first and second liquids has a carboxyl group-containing resin having the aromatic ring, the titanium oxide, and the cyclic ether skeleton. A compound and the photopolymerization initiator.
　上記第１の液が、上記芳香環を有するカルボキシル基含有樹脂を少なくとも含み、かつ、上記第２の液が、上記環状エーテル骨格を有する化合物を少なくとも含むことが好ましい。 It is preferable that the first liquid includes at least a carboxyl group-containing resin having an aromatic ring, and the second liquid includes at least a compound having the cyclic ether skeleton.
　本発明に係るプリント配線板は、回路を表面に有するプリント配線板本体と、該プリント配線板本体の上記回路が設けられた表面に積層されたレジスト膜とを備え、該レジスト膜が、本発明に従って構成された感光性組成物を用いて形成されている。 A printed wiring board according to the present invention includes a printed wiring board main body having a circuit on the surface, and a resist film laminated on the surface of the printed wiring board main body on which the circuit is provided. It is formed using the photosensitive composition comprised according to this.
　本発明に係る感光性組成物は、芳香環を有するカルボキシル基含有樹脂と、酸化チタンと、環状エーテル骨格を有する化合物と、光重合開始剤とを含むので、耐熱クラック性に優れたレジスト膜を得ることができる。 The photosensitive composition according to the present invention includes a carboxyl group-containing resin having an aromatic ring, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator. Obtainable.
　本発明に係る感光性組成物が酸化防止剤を含む場合には、耐熱黄変性に優れたレジスト膜を得ることができる。 When the photosensitive composition according to the present invention contains an antioxidant, a resist film excellent in heat-resistant yellowing can be obtained.
図１は、本発明に係る感光性組成物を用いたレジスト膜を有するＬＥＤデバイスの一例を示す部分切欠正面断面図である。FIG. 1 is a partially cutaway front sectional view showing an example of an LED device having a resist film using the photosensitive composition according to the present invention.
　以下、本発明の詳細を説明する。 Hereinafter, the details of the present invention will be described.
　本発明に係る感光性組成物は、（Ａ）芳香環を有するカルボキシル基含有樹脂と、（Ｂ）酸化チタンと、（Ｃ）環状エーテル骨格を有する化合物と、（Ｄ）光重合開始剤とを含む。 The photosensitive composition according to the present invention comprises (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, (C) a compound having a cyclic ether skeleton, and (D) a photopolymerization initiator. Including.
　（（Ａ）芳香環を有するカルボキシル基含有樹脂）
　本発明に係る感光性組成物に含まれている（Ａ）芳香環を有するカルボキシル基含有樹脂は、芳香環とカルボキシル基とを有するものであれば特に限定されない。（Ａ）芳香環を有するカルボキシルキ含有樹脂として、感光性の不飽和二重結合を少なくとも１つ有する感光性のカルボキシル基含有樹脂、および感光性の不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能である。（Ａ）芳香環を有するカルボキシル基含有樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((A) Carboxyl group-containing resin having an aromatic ring)
The carboxyl group-containing resin having an aromatic ring (A) contained in the photosensitive composition according to the present invention is not particularly limited as long as it has an aromatic ring and a carboxyl group. (A) A carboxyl group-containing resin having an aromatic ring, a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond, and a carboxyl group-containing resin having no photosensitive unsaturated double bond Any of the resins can be used. (A) As for carboxyl group-containing resin which has an aromatic ring, only 1 type may be used and 2 or more types may be used together.
　（Ａ）芳香環を有するカルボキシル基含有樹脂は、下記のカルボキシル基含有樹脂（ａ）～（ｅ）であることが好ましい。下記のカルボキシル基含有樹脂（ａ）～（ｅ）を得る際に、ベンゼン環、置換基を持つベンゼン環、多環芳香環又は複素芳香環を有する化合物が用いられる。上記ベンゼン環に置換した置換基としては、アルキル基、水酸基及び臭素や塩素などのハロゲン原子等が挙げられる。上記多芳香環としては、ナフタレン環やアントラセン環等が挙げられる。上記複素芳香環は、Ｎ、ＳやＯ等を含む。上記複素芳香環としては、ピリジン環、ピロール環、イミダゾール環及びチオフェン環等が挙げられる。 (A) The carboxyl group-containing resin having an aromatic ring is preferably the following carboxyl group-containing resins (a) to (e). In obtaining the following carboxyl group-containing resins (a) to (e), a compound having a benzene ring, a benzene ring having a substituent, a polycyclic aromatic ring or a heteroaromatic ring is used. Examples of the substituent substituted on the benzene ring include alkyl groups, hydroxyl groups, and halogen atoms such as bromine and chlorine. Examples of the polyaromatic ring include a naphthalene ring and an anthracene ring. The heteroaromatic ring includes N, S, O and the like. Examples of the heteroaromatic ring include a pyridine ring, a pyrrole ring, an imidazole ring, and a thiophene ring.
　（ａ）不飽和カルボン酸と重合性不飽和二重結合を有する化合物との共重合によって得られるカルボキシル基含有樹脂
　（ｂ）カルボキシル基含有（メタ）アクリル共重合樹脂（ｂ１）と、１分子中にオキシラン環及びエチレン性重合性不飽和二重結合を有する化合物（ｂ２）との反応により得られるカルボキシル基含有樹脂
　（ｃ）１分子中にそれぞれ１個のエポキシ基及び重合性不飽和二重結合を有する化合物と、重合性不飽和二重結合を有する化合物との共重合体に、不飽和モノカルボン酸を反応させた後、生成した反応物の第２級の水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂
　（ｄ）水酸基含有ポリマーに、飽和又は不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に、１分子中にそれぞれ１個のエポキシ基及び重合性不飽和二重結合を有する化合物を反応させて得られる水酸基及びカルボキシル基含有樹脂
　（ｅ）芳香環を有するエポキシ化合物と飽和多塩基酸無水物や不飽和多塩基酸無水物などの多塩基酸化合物とを反応させて得られる樹脂、又は芳香環を有するエポキシ化合物と不飽和二重結合を少なくとも１つ有するカルボキシル基含有化合物とを反応させた後、飽和多塩基酸無水物や不飽和多塩基酸無水物などの多塩基酸化合物をさらに反応させて得られる樹脂 (A) carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acid and compound having polymerizable unsaturated double bond (b) carboxyl group-containing (meth) acrylic copolymer resin (b1) and in one molecule A carboxyl group-containing resin obtained by reaction with a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond (c) one epoxy group and a polymerizable unsaturated double bond each in one molecule After reacting an unsaturated monocarboxylic acid with a copolymer of a compound having a polymerizable compound and a compound having a polymerizable unsaturated double bond, the secondary hydroxyl group of the resulting reaction product is saturated or unsaturated polybasic. Carboxyl group-containing resin obtained by reacting acid anhydride (d) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is added to one molecule. Hydroxyl and carboxyl group-containing resins obtained by reacting compounds each having one epoxy group and a polymerizable unsaturated double bond (e) Epoxy compounds having aromatic rings and saturated polybasic acid anhydrides and unsaturated compounds A resin obtained by reacting a polybasic acid compound such as a polybasic acid anhydride, or an epoxy compound having an aromatic ring and a carboxyl group-containing compound having at least one unsaturated double bond, and then saturated. Resins obtained by further reacting polybasic acid compounds such as polybasic acid anhydrides and unsaturated polybasic acid anhydrides
　上記芳香環を有するカルボキシル基含有樹脂は、芳香環を有するエポキシ化合物と多塩基酸化合物とを反応させて得られる樹脂、又は芳香環を有するエポキシ化合物と不飽和二重結合を少なくとも１つ有するカルボキシル基含有化合物とを反応させた後、多塩基酸化合物をさらに反応させて得られる樹脂であることが好ましい。この場合には、レジスト膜の耐熱クラック性をより一層高めることができる。 The carboxyl group-containing resin having an aromatic ring is a resin obtained by reacting an epoxy compound having an aromatic ring with a polybasic acid compound, or a carboxyl having at least one unsaturated double bond with an epoxy compound having an aromatic ring. A resin obtained by further reacting a polybasic acid compound after reacting with the group-containing compound is preferred. In this case, the heat crack resistance of the resist film can be further enhanced.
　上記芳香環を有するエポキシ化合物としては、ビスフェノールＡ型、ビスフェノールＦ型、フェノールノボラック型、クレゾールノボラック型、ビフェニル型、ナフタレン型、トリスフェノールメタン型、ジシクロペンタジエン・フェニレン型、フェノール・ビフェニレン型、フェノキシ型、グリシジルアミン型、ビスフェノールＳ型などのエポキシ化合物や、フタル酸ジグリシジルエステル、p-ヒドロキシ安息香酸グリシジル化物などの塩基酸のグリシジルエステル化物や、トリグリシジルイソシアヌレートなどが挙げられる。 Examples of the epoxy compound having an aromatic ring include bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, biphenyl type, naphthalene type, trisphenolmethane type, dicyclopentadiene / phenylene type, phenol / biphenylene type, phenoxy Type, glycidylamine type, bisphenol S type epoxy compounds, glycidyl esterified products of basic acids such as diglycidyl phthalate and glycidyl p-hydroxybenzoate, and triglycidyl isocyanurate.
　（Ａ）芳香環を有するカルボキシル基含有樹脂の酸価は、５０～２００ｍｇＫＯＨ／ｇの範囲内であることが望ましい。酸価が５０ｍｇＫＯＨ／ｇ以上であると、現像時に弱アルカリ水溶液でも未露光部分の除去が容易である。酸価が２００ｍｇＫＯＨ／ｇ以下であると、硬化被膜の耐水性、電気特性がより一層高くなる。また、（Ａ）芳香環を有するカルボキシル基含有樹脂の重量平均分子量は、５，０００～１００，０００の範囲内であることが好ましい。重量平均分子量が５，０００以上であると、指で触れたときの乾燥性がより一層良好になる。また、重量平均分子量が１００，０００以下であると、感光性組成物の露光後の現像性、及び感光性組成物の貯蔵安定性がより一層高くなる。 (A) The acid value of the carboxyl group-containing resin having an aromatic ring is preferably in the range of 50 to 200 mgKOH / g. When the acid value is 50 mgKOH / g or more, unexposed portions can be easily removed even with a weak alkaline aqueous solution during development. When the acid value is 200 mgKOH / g or less, the water resistance and electrical properties of the cured coating are further enhanced. The weight average molecular weight of the (A) carboxyl group-containing resin having an aromatic ring is preferably in the range of 5,000 to 100,000. When the weight average molecular weight is 5,000 or more, the drying property when touched with a finger is further improved. Further, when the weight average molecular weight is 100,000 or less, the developability after exposure of the photosensitive composition and the storage stability of the photosensitive composition are further enhanced.
　上記（Ａ）カルボキシル含有基樹脂は、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有することが望ましい。 The (A) carboxyl-containing group resin includes at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. It is desirable to have one structural unit.
　なお、第１の構造単位や第２の構造単位における芳香環としては、ベンゼン環、置換基を持つベンゼン環、多環芳香環、複素芳香環等が挙げられる。上記ベンゼン環に置換した置換基としては、アルキル基、水酸基及び臭素や塩素などのハロゲン原子等が挙げられる。上記多芳香環としては、ナフタレン環やアントラセン環等が挙げられる。上記複素芳香環は、Ｎ、ＳやＯ等を含む。上記複素芳香環としては、ピリジン環、ピロール環、イミダゾール環及びチオフェン環等が挙げられる。 In addition, examples of the aromatic ring in the first structural unit and the second structural unit include a benzene ring, a benzene ring having a substituent, a polycyclic aromatic ring, and a heteroaromatic ring. Examples of the substituent substituted on the benzene ring include alkyl groups, hydroxyl groups, and halogen atoms such as bromine and chlorine. Examples of the polyaromatic ring include a naphthalene ring and an anthracene ring. The heteroaromatic ring includes N, S, O and the like. Examples of the heteroaromatic ring include a pyridine ring, a pyrrole ring, an imidazole ring, and a thiophene ring.
　上記第１の構造単位を有するカルボキシル基含有樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂や、ビスフェノールＦ型エポキシ樹脂などの第１の構造単位を有する芳香族エポキシ樹脂と、フタル酸、無水フタル酸などの多塩基酸化合物とを反応させて得られるカルボキシル基含有樹脂、又は上記芳香族エポキシ樹脂と（メタ）アクリル酸などの不飽和二重結合を有する塩基酸化合物とを反応させた後、フタル酸、無水フタル酸などの多塩基酸化合物をさらに反応させて得られる不飽和二重結合及びカルボキシル基を含有する樹脂が挙げられる。 Examples of the carboxyl group-containing resin having the first structural unit include an aromatic epoxy resin having a first structural unit such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, or a bisphenol F epoxy resin, A carboxyl group-containing resin obtained by reacting a polybasic acid compound such as phthalic acid or phthalic anhydride, or the above-mentioned aromatic epoxy resin and a basic acid compound having an unsaturated double bond such as (meth) acrylic acid Examples of the resin include an unsaturated double bond and a carboxyl group obtained by further reacting with a polybasic acid compound such as phthalic acid or phthalic anhydride after the reaction.
　上記第２の構造単位を有するカルボキシル基含有樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂や、ビスフェノールＡ型エポキシ樹脂などの芳香族エポキシ樹脂と、フタル酸、無水フタル酸などの多塩基酸化合物とを反応させて得られるカルボキシル基含有樹脂、又は上記芳香族エポキシ樹脂と、（メタ）アクリル酸などの不飽和二重結合を有する塩基酸化合物とを反応させた後、フタル酸、無水フタル酸などの多塩基酸化合物をさらに反応させて得られる不飽和二重結合及びカルボキシル基を含有する樹脂が挙げられる。（Ａ）カルボキシル基含有樹脂が、上記第１の構造単位及び上記第２の構造単位の内の少なくとも１つの構造単位を有する場合には、レジスト膜の耐熱黄変性及び耐熱クラック性をさらに一層高めることができる。 Examples of the carboxyl group-containing resin having the second structural unit include an aromatic epoxy resin such as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, and a phthalate. A carboxyl group-containing resin obtained by reacting an acid, a polybasic acid compound such as phthalic anhydride, or the above aromatic epoxy resin, and a basic acid compound having an unsaturated double bond such as (meth) acrylic acid Examples of the resin include an unsaturated double bond and a carboxyl group obtained by further reacting with a polybasic acid compound such as phthalic acid or phthalic anhydride after the reaction. (A) When the carboxyl group-containing resin has at least one of the first structural unit and the second structural unit, the heat yellowing resistance and crack resistance of the resist film are further enhanced. be able to.
　上記第１の構造単位における２つの芳香環は、ベンゼン環または置換基を持つベンゼン環であることが好ましい。上記第１の構造単位は、下記式（１１）で表される構造単位であることが好ましい。下記式（１１）中に示された共有結合は、フェニレン基に対してどの位置に結合していてもよい。また、フェニレン基は置換されていてもよい。 The two aromatic rings in the first structural unit are preferably a benzene ring or a benzene ring having a substituent. The first structural unit is preferably a structural unit represented by the following formula (11). The covalent bond shown in the following formula (11) may be bonded at any position with respect to the phenylene group. The phenylene group may be substituted.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記第２の構造単位における芳香環は、ベンゼン環または置換基を持つベンゼン環であることが好ましい。第２の構造単位は、下記式（１２）で表される構造単位であることが好ましい。下記式（１２）中に示された共有結合は、フェニレン基に対してどの位置に結合していてもよい。また、フェニレン基は置換されていてもよい。 The aromatic ring in the second structural unit is preferably a benzene ring or a benzene ring having a substituent. The second structural unit is preferably a structural unit represented by the following formula (12). The covalent bond shown in the following formula (12) may be bonded at any position with respect to the phenylene group. The phenylene group may be substituted.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　本発明に係る感光性組成物が、フェノール系酸化防止剤を含まないか、又はフェノール系酸化防止剤をさらに含み、上記芳香環を有するカルボキシル基含有樹脂が、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有し、上記酸化チタンが、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含まないか、又は該ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含み、上記芳香環を有するカルボキシル基含有樹脂の上記第１の構造単位のモル数をＶとし、上記芳香環を有するカルボキシル基含有樹脂の上記第２の構造単位のモル数をＷとし、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンのモル数をＸ１とし、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンではない酸化チタンのモル数をＸ２とし、かつ上記フェノール系酸化防止剤のフェノール基のモル数をＹとしたときに、本発明に係る感光性組成物は、下記式（１）を満たすことが好ましい。 The photosensitive composition according to the present invention does not contain a phenolic antioxidant or further contains a phenolic antioxidant, and the carboxyl group-containing resin having an aromatic ring has two aromatic rings via a methylene group. And at least one structural unit of the second structural unit in which the oxymethylene group and the aromatic ring are ether-bonded, and the titanium oxide is formed by a silicon oxide or a silicone compound. The first structural unit of the carboxyl group-containing resin not containing surface-treated rutile-type titanium oxide or containing rutile-type titanium oxide surface-treated with the silicon oxide or silicone compound and having the aromatic ring The number of moles is V, the number of moles of the second structural unit of the carboxyl group-containing resin having an aromatic ring is W, and the silicon oxide or X1 is the number of moles of rutile titanium oxide surface-treated with a silicone compound, X2 is the number of moles of titanium oxide that is not a rutile titanium oxide surface-treated with the above silicon oxide or silicone compound, and the above phenolic oxidation. When the number of moles of phenol groups in the inhibitor is Y, the photosensitive composition according to the present invention preferably satisfies the following formula (1).
　０．０６≦（５Ｖ＋３Ｗ）／（３Ｘ１＋Ｘ２＋１００Ｙ）≦０．３５　・・・式（１） 0.06 ≦ (5V + 3W) / (3X1 + X2 + 100Y) ≦ 0.35 Expression (1)
　上記式（１）を満たす場合、レジスト膜の耐熱黄変性をより一層高めると共に耐熱クラック性を高めることができる。 When the above formula (1) is satisfied, the heat yellowing resistance of the resist film can be further enhanced and the heat cracking resistance can be enhanced.
　（（Ｂ）酸化チタン）
　本発明に係る感光性組成物に含まれている（Ｂ）酸化チタンは特に限定されない。（Ｂ）酸化チタンは、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((B) Titanium oxide)
The (B) titanium oxide contained in the photosensitive composition according to the present invention is not particularly limited. (B) As for titanium oxide, only 1 type may be used and 2 or more types may be used together.
　（Ｂ）酸化チタンを用いた場合には、酸化チタン以外の他の無機フィラーを用いた場合と比較して、反射率が高いレジスト膜を形成できる。 (B) When titanium oxide is used, a resist film having a high reflectance can be formed as compared with the case where other inorganic fillers other than titanium oxide are used.
　（Ｂ）酸化チタンは、ルチル型酸化チタン又はアナターゼ型酸化チタンであることが好ましい。ルチル型酸化チタンの使用により、耐熱黄変性により一層優れたレジスト膜を形成できる。上記アナターゼ型酸化チタンは、ルチル型酸化チタンよりも、硬度が低い。このため、アナターゼ型酸化チタンの使用により、レジスト膜の加工性を高めることができる。 (B) The titanium oxide is preferably rutile titanium oxide or anatase titanium oxide. By using rutile type titanium oxide, a more excellent resist film can be formed by heat-resistant yellowing. The anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. For this reason, the use of anatase-type titanium oxide can improve the processability of the resist film.
　上記酸化チタンは、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含むことが望ましい。上記酸化チタン１００重量％中、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンの含有量は１０重量％以上であることが望ましく、３０重量％以上であることがより望ましい。上記酸化チタンは、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンであることがより望ましい。これらの場合には、レジスト膜の耐熱黄変性をより一層高めることができる。 The titanium oxide preferably contains rutile titanium oxide surface-treated with silicon oxide or a silicone compound. In 100% by weight of the titanium oxide, the content of the rutile titanium oxide surface-treated with the silicon oxide or the silicone compound is desirably 10% by weight or more, and more desirably 30% by weight or more. The titanium oxide is more preferably rutile titanium oxide surface-treated with the silicon oxide or silicone compound. In these cases, the heat-resistant yellowing of the resist film can be further enhanced.
　ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンとしては、例えば、ルチル塩素法酸化チタンである石原産業社製の品番：ＣＲ－９０や、ルチル硫酸法酸化チタンである石原産業社製の品番：Ｒ－５５０等が挙げられる。 Examples of the rutile type titanium oxide surface-treated with silicon oxide or silicone compound include, for example, product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is rutile chlorine method titanium oxide, and manufactured by Ishihara Sangyo Co., Ltd., which is rutile sulfuric acid method titanium oxide. Product number: R-550 and the like.
　本発明に係る感光性組成物１００重量％中、（Ｂ）酸化チタンの含有量は、３重量％以上８０重量％以下であることが好ましい。（Ｂ）酸化チタンの含有量の好ましい下限は１０重量％、好ましい上限は７５重量％である。（Ｂ）酸化チタンの含有量が上記範囲内にあると、レジスト膜が高温に晒されたときに、黄変し難くなる。さらに、塗工に適した粘度を有する感光性組成物を容易に調製できる。 In 100% by weight of the photosensitive composition according to the present invention, the content of (B) titanium oxide is preferably 3% by weight or more and 80% by weight or less. (B) The minimum with preferable content of titanium oxide is 10 weight%, and a preferable upper limit is 75 weight%. (B) When the content of titanium oxide is within the above range, yellowing hardly occurs when the resist film is exposed to a high temperature. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.
　（（Ｃ）環状エーテル骨格を有する化合物）
　本発明に係る感光性組成物に含まれている（Ｃ）環状エーテル骨格を有する化合物は、環状エーテル骨格を有していれば特に限定されない。（Ｃ）環状エーテル骨格を有する化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((C) Compound having cyclic ether skeleton)
The compound (C) having a cyclic ether skeleton contained in the photosensitive composition according to the present invention is not particularly limited as long as it has a cyclic ether skeleton. (C) As for the compound which has cyclic ether frame | skeleton, only 1 type may be used and 2 or more types may be used together.
　（Ｃ）環状エーテル骨格を有する化合物としては、例えば、ビスフェノールＳ型エポキシ樹脂、ジグリシジルフタレート樹脂、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、テトラグリシジルキシレノイルエタン樹脂、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ビスフェノールＡのノボラック型エポキシ樹脂、キレート型エポキシ樹脂、グリオキザール型エポキシ樹脂、アミノ基含有エポキシ樹脂、ゴム変性エポキシ樹脂、ジシクロペンタジエンフェノリック型エポキシ樹脂、シリコーン変性エポキシ樹脂や、ε－カプロラクトン変性エポキシ樹脂が挙げられる。 (C) Examples of compounds having a cyclic ether skeleton include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, and tetraglycidyl. Xylenoylethane resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin Bisphenol A novolac epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol Click type epoxy resin, and silicone-modified epoxy resins, and ε- caprolactone modified epoxy resin.
　（Ｃ）環状エーテル骨格を有する化合物は、芳香環を有することが好ましい。この場合には、レジスト膜の耐熱クラック性をより一層高めることができる。 (C) The compound having a cyclic ether skeleton preferably has an aromatic ring. In this case, the heat crack resistance of the resist film can be further enhanced.
　上記芳香環を有するエポキシ化合物としては、ビスフェノールＡ型、ビスフェノールＦ型、フェノールノボラック型、クレゾールノボラック型、ビフェニル型、ナフタレン型、トリスフェノールメタン型、ジシクロペンタジエン・フェニレン型、フェノール・ビフェニレン型、フェノキシ型、グリシジルアミン型、ビスフェノールＳ型などのエポキシ化合物や、フタル酸ジグリシジルエステル、p-ヒドロキシ安息香酸グリシジル化物などの塩基酸のグリシジルエステル化物や、トリグリシジルイソシアヌレートなどが挙げられる。 Examples of the epoxy compound having an aromatic ring include bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, biphenyl type, naphthalene type, trisphenolmethane type, dicyclopentadiene / phenylene type, phenol / biphenylene type, phenoxy Type, glycidylamine type, bisphenol S type epoxy compounds, glycidyl esterified products of basic acids such as diglycidyl phthalate and glycidyl p-hydroxybenzoate, and triglycidyl isocyanurate.
　（Ｃ）環状エーテル骨格を有する化合物は、（Ａ）カルボキシル基含有樹脂のカルボキシル基と反応して、感光性組成物を硬化させるように作用する。 (C) The compound having a cyclic ether skeleton reacts with the carboxyl group of the (A) carboxyl group-containing resin to act to cure the photosensitive composition.
　（Ａ）芳香環を有するカルボキシル基含有樹脂１００重量部に対して、（Ｃ）環状エーテル骨格を有する化合物の含有量の好ましい下限は０．１重量部、より好ましい下限は１重量部、好ましい上限は５０重量部、より好ましい上限は３０重量部である。（Ｃ）環状エーテル骨格を有する化合物の含有量が上記好ましい上限及び下限を満たすと、レジスト膜の黄変をより一層抑制できる。 (A) The preferable lower limit of the content of the compound (C) having a cyclic ether skeleton is 0.1 parts by weight, and the more preferable lower limit is 1 part by weight, with respect to 100 parts by weight of the carboxyl group-containing resin having an aromatic ring. Is 50 parts by weight, and a more preferred upper limit is 30 parts by weight. (C) If content of the compound which has cyclic ether frame | skeleton satisfy | fills the said preferable upper limit and minimum, yellowing of a resist film can be suppressed further.
　（（Ｄ）光重合開始剤）
　本発明に係る感光性組成物は（Ｄ）光重合開始剤を含むため、感光性を有する。（Ｄ）光重合開始剤は特に限定されない。（Ｄ）光重合開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((D) Photopolymerization initiator)
Since the photosensitive composition which concerns on this invention contains the photoinitiator (D), it has photosensitivity. (D) The photopolymerization initiator is not particularly limited. (D) As for a photoinitiator, only 1 type may be used and 2 or more types may be used together.
　（Ｄ）光重合開始剤としては、例えば、アシルフォスフィンオキサイド、ハロメチル化トリアジン、ハロメチル化オキサジアゾール、イミダゾール、ベンゾイン、ベンゾインアルキルエーテル、アントラキノン、ベンズアンスロン、ベンゾフェノン、アセトフェノン、チオキサントン、安息香酸エステル、アクリジン、フェナジン、チタノセン、α－アミノアルキルフェノン、オキシムや、これらの誘導体等が挙げられる。 (D) As the photopolymerization initiator, for example, acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, benzoate, Examples thereof include acridine, phenazine, titanocene, α-aminoalkylphenone, oxime, and derivatives thereof.
　（Ａ）芳香環を有するカルボキシル基含有樹脂１００重量部に対して、（Ｄ）光重合開始剤の含有量の好ましい下限は０．１重量部、より好ましい下限は１重量部、好ましい上限は３０重量部、より好ましい上限は１５重量部である。（Ｄ）光重合開始剤の含有量が上記好ましい下限及び上限を満たすと、感光性組成物の感光性をより一層高めることができる。 (A) The preferable lower limit of the content of the photopolymerization initiator (D) is 0.1 parts by weight, the more preferable lower limit is 1 part by weight, and the preferable upper limit is 30 parts per 100 parts by weight of the carboxyl group-containing resin having an aromatic ring. Part by weight, more preferred upper limit is 15 parts by weight. (D) When content of a photoinitiator satisfy | fills the said preferable minimum and upper limit, the photosensitivity of a photosensitive composition can be improved further.
　（（Ｅ）希釈剤）
　本発明に係る感光性組成物は、（Ｅ）希釈剤を含むことが好ましい。（Ｅ）希釈剤の使用により、感光性組成物を塗工しやすくすることができる。（Ｅ）希釈剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((E) Diluent)
The photosensitive composition according to the present invention preferably contains (E) a diluent. (E) By using a diluent, the photosensitive composition can be easily applied. (E) As for a diluent, only 1 type may be used and 2 or more types may be used together.
　（Ｅ）希釈剤は、感光性組成物の粘度を調整して作業性を向上させるとともに、架橋密度を高くしたり、密着性などを向上したりするために用いられる。（Ｅ）希釈剤として、光重合性モノマーなどの反応性希釈剤や、公知慣用の溶剤を使用できる。該溶剤としては、有機溶剤や、水等が挙げられる。 (E) The diluent is used to adjust the viscosity of the photosensitive composition to improve workability, to increase the crosslink density, and to improve adhesion. (E) As a diluent, reactive diluents, such as a photopolymerizable monomer, and a well-known usual solvent can be used. Examples of the solvent include organic solvents and water.
　上記光重合性モノマーとしては、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート類、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレンオキシド誘導体のモノ又はジ（メタ）アクリレート類、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリスヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキシド又はプロピレンオキシド付加物の多価（メタ）アクリレート類、フェノキシエチル（メタ）アクリレート、ビスフェノールＡのポリエトキシジ（メタ）アクリレート等のフェノール類のエチレンオキシド又はプロピレンオキシド付加物の（メタ）アクリレート類、グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリジジルエーテルの（メタ）アクリレート類や、メラミン（メタ）アクリレート等が挙げられる。これらの光重合性モノマーは、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the photopolymerizable monomer include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate, and hydroxy such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Alkyl (meth) acrylates, mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol , Polyhydric alcohols such as trishydroxyethyl isocyanurate or poly (meth) acrylates of these ethylene oxide or propylene oxide adducts (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as rate, phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl (Meth) acrylates of glycidyl ether such as isocyanurate, melamine (meth) acrylate, and the like. As for these photopolymerizable monomers, only 1 type may be used and 2 or more types may be used together.
　感光性組成物の液安定性を高める観点からは、親水性基を有する（メタ）アクリレート類が好ましい。また、感光性組成物の光硬化性を高める観点からは、多官能性の（メタ）アクリレート類が好ましい。上記感光性組成物１００重量％中、上記光重合モノマーの含有量の好ましい上限は２０重量％、より好ましい上限は１０重量％である。上記光重合性モノマーの含有量が上記好ましい上限を満たすと、硬化物の表面のべたつきが少なく、指で触れたときの乾燥性が良好になる。 From the viewpoint of improving the liquid stability of the photosensitive composition, (meth) acrylates having a hydrophilic group are preferred. Moreover, from a viewpoint of improving the photocurability of the photosensitive composition, polyfunctional (meth) acrylates are preferable. In 100% by weight of the photosensitive composition, a preferable upper limit of the content of the photopolymerizable monomer is 20% by weight, and a more preferable upper limit is 10% by weight. When content of the said photopolymerizable monomer satisfy | fills the said preferable upper limit, there is little stickiness of the surface of hardened | cured material and drying property when touched with a finger will become favorable.
　上記有機溶剤としては、メチルエチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類、オクタン、デカン等の脂肪族炭化水素類、並びに石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤等が挙げられる。上記有機溶剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate , Esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, and petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha. As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.
　（Ｅ）希釈剤の含有量は特に限定されない。感光性組成物の塗工性を考慮して、（Ｅ）希釈剤は適宜の含有量で用いられる。 (E) The content of the diluent is not particularly limited. In consideration of the coating property of the photosensitive composition, the (E) diluent is used in an appropriate content.
　（（Ｆ）酸化防止剤）
　高温に晒されたときにレジスト膜が黄変するおそれを小さくするために、本発明に係る感光性組成物は、（Ｆ）酸化防止剤を含むことが好ましい。（Ｆ）酸化防止剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 ((F) Antioxidant)
In order to reduce the risk of yellowing of the resist film when exposed to a high temperature, the photosensitive composition according to the present invention preferably contains (F) an antioxidant. (F) As for antioxidant, only 1 type may be used and 2 or more types may be used together.
　（Ｆ）酸化防止剤は、ルイス塩基性部位を有することが好ましい。レジスト膜の黄変をより一層抑制する観点からは、（Ｆ）酸化防止剤は、フェノール系酸化防止剤、リン系酸化防止剤や、アミン系酸化防止剤からなる群から選択された少なくとも一種であることが好ましい。レジスト膜の黄変をさらに一層抑制する観点からは、（Ｆ）酸化防止剤は、フェノール系酸化防止剤であることが好ましい。 (F) The antioxidant preferably has a Lewis basic moiety. From the viewpoint of further suppressing the yellowing of the resist film, (F) the antioxidant is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Preferably there is. From the viewpoint of further suppressing the yellowing of the resist film, the (F) antioxidant is preferably a phenolic antioxidant.
　上記フェノール系酸化防止剤の市販品としては、ＩＲＧＡＮＯＸ　１０１０、ＩＲＧＡＮＯＸ　１０３５、ＩＲＧＡＮＯＸ　１０７６、ＩＲＧＡＮＯＸ　１１３５、ＩＲＧＡＮＯＸ　２４５、ＩＲＧＡＮＯＸ　２５９や、ＩＲＧＡＮＯＸ　２９５（以上、いずれもチバ・ジャパン社製）、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－７０、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－９０や、アデカスタブ　ＡＯ－３３０（以上、いずれもＡＤＥＫＡ社製）、Ｓｕｍｉｌｉｚｅｒ　ＧＡ－８０、Ｓｕｍｉｌｉｚｅｒ　ＭＤＰ－Ｓ、Ｓｕｍｉｌｉｚｅｒ　ＢＢＭ－Ｓ、Ｓｕｍｉｌｉｚｅｒ　ＧＭ、Ｓｕｍｉｌｉｚｅｒ　ＧＳ（Ｆ）や、Ｓｕｍｉｌｉｚｅｒ　ＧＰ（以上、いずれも住友化学工業社製）、ＨＯＳＴＡＮＯＸ　Ｏ１０、ＨＯＳＴＡＮＯＸ　Ｏ１６、ＨＯＳＴＡＮＯＸ　Ｏ１４や、ＨＯＳＴＡＮＯＸ　Ｏ３（以上、いずれもクラリアント社製）、アンテージ　ＢＨＴ、アンテージ　Ｗ－３００、アンテージ　Ｗ－４００や、アンテージ　Ｗ５００（以上、いずれも川口化学工業社製）、並びにＳＥＥＮＯＸ　２２４Ｍや、ＳＥＥＮＯＸ　３２６Ｍ（以上、いずれもシプロ化成社製）等が挙げられる。 Commercially available products of the above-mentioned phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295 (all of which are manufactured by Ciba Japan), Adeka Stub AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sum riser GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, HOSTANOX O3 (all of which are manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, Antage W500 (above, all manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, SEENOX 326M (above, both manufactured by Sipro Kasei Co., Ltd.) and the like.
　上記リン系酸化防止剤としては、シクロヘキシルフォスフィンや、トリフェニルフォスフィン等が挙げられる。上記リン系酸化防止剤の市販品としては、アデアスタブ　ＰＥＰ－４Ｃ、アデアスタブ　ＰＥＰ－８、アデアスタブ　ＰＥＰ－２４Ｇ、アデアスタブ　ＰＥＰ－３６、アデアスタブ　ＨＰ－１０、アデアスタブ　２１１２、アデアスタブ　２６０、アデアスタブ　５２２Ａ、アデアスタブ　１１７８、アデアスタブ　１５００、アデアスタブ　Ｃ、アデアスタブ　１３５Ａ、アデアスタブ　３０１０や、アデアスタブ　ＴＰＰ（以上、いずれもＡＤＥＫＡ社製）、サンドスタブ　Ｐ－ＥＰＱや、ホスタノックス　ＰＡＲ２４（以上、いずれもクラリアント社製）、並びにＪＰ－３１２Ｌ、ＪＰ－３１８－０、ＪＰＭ－３０８、ＪＰＭ－３１３、ＪＰＰ－６１３Ｍ、ＪＰＰ－３１、ＪＰＰ－２０００ＰＴや、ＪＰＨ－３８００（以上、いずれも城北化学工業社製）等が挙げられる。 Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Commercially available products of the above-mentioned phosphoric antioxidants include Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, 1500, Adeastab C, Adeastab 135A, Adeastab 3010, Adeastab TPP (all made by ADEKA), Sandstub P-EPQ, Hostanox PAR24 (all made by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, JPH-3800 (all of these Kitakagaku Kogyo Co., Ltd.), and the like.
　上記アミン系酸化防止剤としては、トリエチルアミン、ジシアンジアミド、メラミン、エチルジアミノ－Ｓ－トリアジン、２，４－ジアミノ－Ｓ－トリアジン、２，４－ジアミノ－６－トリル－Ｓ－トリアジン、２，４－ジアミノ－６－キシリル－Ｓ－トリアジンや、第四級アンモニウム塩誘導体等が挙げられる。 Examples of the amine antioxidant include triethylamine, dicyandiamide, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine, 2,4- Examples thereof include diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.
　（Ａ）芳香環を有するカルボキシル基含有樹脂１００重量部に対して、（Ｆ）酸化防止剤の含有量の好ましい下限は０．１重量部、より好ましい下限は５重量部、好ましい上限は３０重量部、より好ましい上限は１５重量部である。（Ｆ）酸化防止剤の含有量が上記好ましい下限及び上限を満たすと、耐熱黄変性により一層優れたレジスト膜を形成できる。 (A) With respect to 100 parts by weight of the carboxyl group-containing resin having an aromatic ring, the preferred lower limit of the content of (F) antioxidant is 0.1 parts by weight, the more preferred lower limit is 5 parts by weight, and the preferred upper limit is 30 parts by weight. Parts, more preferred upper limit is 15 parts by weight. (F) When the content of the antioxidant satisfies the above preferable lower limit and upper limit, a more excellent resist film can be formed by heat-resistant yellowing.
　（その他の成分）
　本発明に係る感光性組成物は、着色剤、充填剤、消泡剤、硬化剤、硬化促進剤、離型剤、表面処理剤、難燃剤、粘度調節剤、分散剤、分散助剤、表面改質剤、可塑剤、抗菌剤、防黴剤、レベリング剤、安定剤、カップリング剤、タレ防止剤又は蛍光体等を含んでいてもよい。 (Other ingredients)
The photosensitive composition according to the present invention includes a colorant, a filler, an antifoaming agent, a curing agent, a curing accelerator, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface. It may contain a modifier, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent or a phosphor.
　（感光性組成物及びその調製方法）
　本発明に係る感光性組成物は、１液型の感光性組成物であってもよい。さらに、本発明に係る感光性組成物は、フィルム状の感光性組成物であってもよい。感光性組成物をフィルム状にする方法として、公知の方法を用いることができる。なお、フィルムにはシート含まれる。 (Photosensitive composition and preparation method thereof)
The photosensitive composition according to the present invention may be a one-component type photosensitive composition. Furthermore, the photosensitive composition according to the present invention may be a film-like photosensitive composition. A known method can be used as a method for forming the photosensitive composition into a film. The film includes a sheet.
　さらに、本発明に係る感光性組成物は、第１の液と、第２の液とを有し、該第１，第２の液が混合されて用いられる２液混合型の感光性組成物であってもよい。２液混合型の感光性組成物の場合には、使用前に重合又は硬化反応が進行するのを抑制できる。このため、２液それぞれのポットライフを向上できる。 Furthermore, the photosensitive composition according to the present invention has a first liquid and a second liquid, and the two-liquid mixed photosensitive composition used by mixing the first and second liquids. It may be. In the case of a two-component mixed photosensitive composition, the progress of polymerization or curing reaction before use can be suppressed. For this reason, the pot life of each of the two liquids can be improved.
　２液混合型の感光性組成物の場合には、（Ａ）芳香環を有するカルボキシル基含有樹脂と、（Ｂ）酸化チタンと、（Ｃ）環状エーテル骨格を有する化合物と、（Ｄ）光重合開始剤とはそれぞれ、上記第１の液及び上記第２の液の内の少なくとも一方に含まれる。 In the case of a two-component mixed photosensitive composition, (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, (C) a compound having a cyclic ether skeleton, and (D) photopolymerization. Each initiator is included in at least one of the first liquid and the second liquid.
　上記第１，第２の液が混合された混合物は、感光性組成物であり、（Ａ）芳香環を有するカルボキシル基含有樹脂と、（Ｂ）酸化チタンと、（Ｃ）環状エーテル骨格を有する化合物と、（Ｄ）光重合開始剤とを含む。 The mixture in which the first and second liquids are mixed is a photosensitive composition having (A) a carboxyl group-containing resin having an aromatic ring, (B) titanium oxide, and (C) a cyclic ether skeleton. A compound and (D) a photopolymerization initiator.
　２液それぞれのポットライフをより一層高める観点からは、上記第１の液が、（Ａ）芳香環を有するカルボキシル基含有樹脂を少なくとも含み、かつ上記第２の液が、（Ｃ）環状エーテル骨格を有する化合物を少なくとも含むことが好ましい。上記第１の液が、（Ｃ）環状エーテル骨格を有する化合物を含まず、（Ａ）芳香環を有するカルボキシル基含有樹脂を少なくとも含み、かつ上記第２の液が、（Ａ）芳香環を有するカルボキシル基含有樹脂を含まず、（Ｃ）環状エーテル骨格を有する化合物を少なくとも含むことがより好ましい。すなわち、（Ａ）芳香環を有するカルボキシル基含有樹脂と（Ｃ）環状エーテル骨格を有する化合物とが、同じ液に含まれておらず、異なる液に含まれていることがより好ましい。 From the viewpoint of further increasing the pot life of each of the two liquids, the first liquid includes at least (A) a carboxyl group-containing resin having an aromatic ring, and the second liquid includes (C) a cyclic ether skeleton. It is preferable to include at least a compound having The first liquid does not include (C) a compound having a cyclic ether skeleton, includes (A) a carboxyl group-containing resin having an aromatic ring, and the second liquid has (A) an aromatic ring. More preferably, it does not include a carboxyl group-containing resin and includes (C) a compound having a cyclic ether skeleton. That is, it is more preferable that (A) the carboxyl group-containing resin having an aromatic ring and (C) the compound having a cyclic ether skeleton are not contained in the same liquid but contained in different liquids.
　本発明に係る感光性組成物は、例えば、各配合成分を撹拌混合した後、３本ロールにて均一に混合することにより調製できる。 The photosensitive composition according to the present invention can be prepared, for example, by stirring and mixing the ingredients and then uniformly mixing with three rolls.
　感光性組成物を硬化させるために使用される光源としては、紫外線又は可視光線等の活性エネルギー線を発光する照射装置が挙げられる。上記光源として、例えば、超高圧水銀灯、Ｄｅｅｐ　ＵＶ　ランプ、高圧水銀灯、低圧水銀灯、メタルハライドランプや、エキシマレーザーが挙げられる。これらの光源は、感光性組成物の構成成分の感光波長に応じて適宜選択される。光の照射エネルギーは、所望とする膜厚又は感光性組成物の構成成分により適宜選択される。光の照射エネルギーは、一般に、１０～３０００ｍＪ／ｃｍ２の範囲内である。 Examples of the light source used for curing the photosensitive composition include an irradiation device that emits active energy rays such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources are appropriately selected according to the photosensitive wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness or the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm 2 .
　（プリント配線板及びＬＥＤデバイス）
　本発明に係る感光性組成物は、プリント配線板のレジスト膜を形成する用途に好適に用いられ、ソルダーレジスト膜を形成する用途により好適に用いられる。本発明に係る感光性組成物は、レジスト組成物であることが好ましく、ソルダーレジスト組成物であることがより好ましい。 (Printed wiring boards and LED devices)
The photosensitive composition concerning this invention is used suitably for the use which forms the resist film of a printed wiring board, and is used suitably by the use which forms a soldering resist film. The photosensitive composition according to the present invention is preferably a resist composition, and more preferably a solder resist composition.
　本発明に係るプリント配線板は、回路を表面に有するプリント配線板本体と、該プリント配線板本体の上記回路が設けられた表面に積層されたレジスト膜とを備える。該レジスト膜が、本発明に係る感光性組成物により形成されている。 The printed wiring board according to the present invention includes a printed wiring board body having a circuit on the surface, and a resist film laminated on the surface of the printed wiring board body on which the circuit is provided. The resist film is formed of the photosensitive composition according to the present invention.
　本発明に係る感光性組成物は、ＬＥＤチップが基板に実装されているＬＥＤデバイス中のレジスト膜の形成に好適に用いられ、ソルダーレジスト膜の形成により好適に用いられる。 The photosensitive composition according to the present invention is suitably used for forming a resist film in an LED device in which an LED chip is mounted on a substrate, and is preferably used for forming a solder resist film.
　図１は、本発明に係る感光性組成物を用いて形成されたソルダーレジスト膜を備えるＬＥＤデバイスの一例を模式的に示す部分切欠正面断面図である。 FIG. 1 is a partially cutaway front sectional view schematically showing an example of an LED device including a solder resist film formed using the photosensitive composition according to the present invention.
　図１に示すＬＥＤデバイス１では、基板２上に、ソルダーレジスト膜３が形成されている。ソルダーレジスト膜３上に、ＬＥＤチップ７が搭載されている。 In the LED device 1 shown in FIG. 1, a solder resist film 3 is formed on a substrate 2. An LED chip 7 is mounted on the solder resist film 3.
　基板２は、ガラス層５と樹脂層６とを有する積層基板である。基板２は、特に限定されず、樹脂と他の材料からなる積層基板に限らず、セラミック多層基板などの他の積層基板により形成されていてもよい。さらに、基板２は、単一の樹脂材料からなる樹脂基板であってもよい。基板２上には、電極４ａ，４ｂが形成されている。電極４ａ，４ｂは、適宜の金属もしくは合金からなる。回路としての電極４ａ，４ｂが上面に形成された基板２は、プリント配線板本体である。 The substrate 2 is a laminated substrate having a glass layer 5 and a resin layer 6. The board | substrate 2 is not specifically limited, Not only the laminated board which consists of resin and another material, You may be formed with other laminated boards, such as a ceramic multilayer board | substrate. Further, the substrate 2 may be a resin substrate made of a single resin material. Electrodes 4 a and 4 b are formed on the substrate 2. The electrodes 4a and 4b are made of an appropriate metal or alloy. The substrate 2 on which the electrodes 4a and 4b as circuits are formed on the upper surface is a printed wiring board body.
　ソルダーレジスト膜３は、本発明の感光性組成物を基板２上に塗工し、露光し、現像することにより形成されている。より具体的には、電極４ａ，４ｂを形成した後に、基板２上の全領域に感光性組成物を塗工する。次に、下方に電極４ａ，４ｂが位置する部分が遮光部とされているマスクを用いて感光性組成物を上方から選択的に露光する。露光により、光が照射された領域では、感光性組成物が硬化する。遮光部で覆われた領域では感光性組成物の硬化は進行しない。従って、硬化していない感光性組成物を溶解する溶剤を用いて、露光されていない感光性組成物部分を除去する。このようにして、図１に示す開口部３ａ，３ｂを有するソルダーレジスト膜３を得ることができる。開口部３ａ，３ｂには、電極４ａ，４ｂがそれぞれ露出している。 The solder resist film 3 is formed by coating the photosensitive composition of the present invention on the substrate 2, exposing and developing. More specifically, after forming the electrodes 4 a and 4 b, the photosensitive composition is applied to the entire region on the substrate 2. Next, the photosensitive composition is selectively exposed from above using a mask in which the portions where the electrodes 4a and 4b are located are light shielding portions. The photosensitive composition is cured in a region irradiated with light by exposure. Curing of the photosensitive composition does not proceed in the region covered with the light shielding part. Therefore, the unexposed photosensitive composition portion is removed using a solvent that dissolves the uncured photosensitive composition. In this way, the solder resist film 3 having the openings 3a and 3b shown in FIG. 1 can be obtained. The electrodes 4a and 4b are exposed in the openings 3a and 3b, respectively.
　次に、下面７ａに端子８ａ，８ｂを有するＬＥＤチップ７をソルダーレジスト膜３上に搭載し、半田９ａ，９ｂにより端子８ａ，８ｂと電極４ａ，４ｂとをそれぞれ接合する。このようにして、ＬＥＤデバイス１が得られる。 Next, the LED chip 7 having the terminals 8a and 8b on the lower surface 7a is mounted on the solder resist film 3, and the terminals 8a and 8b and the electrodes 4a and 4b are joined by solders 9a and 9b, respectively. In this way, the LED device 1 is obtained.
　ＬＥＤデバイス１では、ＬＥＤチップ７を駆動すると、破線で示すように光が発せられる。この場合、ＬＥＤチップ７から基板２の上面２ａとは反対側すなわち上方に照射される光だけでなく、ソルダーレジスト膜３に到達した光が矢印Ａで示すように反射される。ソルダーレジスト膜３は、白色であり、上記光を高い効率で反射させる。従って、矢印Ａで示す反射光も利用されるので、ＬＥＤチップ７の光の利用効率を高めることができる。 In the LED device 1, when the LED chip 7 is driven, light is emitted as indicated by a broken line. In this case, not only the light irradiated from the LED chip 7 to the side opposite to the upper surface 2a of the substrate 2, that is, the light irradiated on the upper side, but also the light reaching the solder resist film 3 is reflected as indicated by an arrow A. The solder resist film 3 is white and reflects the light with high efficiency. Therefore, since the reflected light indicated by the arrow A is also used, the light use efficiency of the LED chip 7 can be increased.
　以下、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。本発明は、以下の実施例に限定されない。 Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.
　まず、下記の合成例１～８により、（Ａ１）～（Ａ７）の芳香環を有するカルボキシル基含有樹脂、並びに芳香環を有さないカルボキシル基含有樹脂を用意した。合成例１、６、７で得られるカルボキシル基含有樹脂は、第１および第２の構造単位を有するカルボキシル基含有樹脂に相当する。合成例５、８で得られるカルボキシル基含有樹脂は、第２の構造単位を有するカルボキシル基含有樹脂に相当する。 First, according to Synthesis Examples 1 to 8 below, a carboxyl group-containing resin having an aromatic ring (A1) to (A7) and a carboxyl group-containing resin having no aromatic ring were prepared. The carboxyl group-containing resins obtained in Synthesis Examples 1, 6, and 7 correspond to the carboxyl group-containing resins having the first and second structural units. The carboxyl group-containing resins obtained in Synthesis Examples 5 and 8 correspond to the carboxyl group-containing resin having the second structural unit.
　（合成例１）
　エチルカルビトールアセテート１３９重量部中で、触媒としてジメチルベンジルアミン０．５重量部と、重合禁止剤としてハイドロキノン０．１重量部とを用いて、エポキシ当量２１０、軟化点８０℃のクレゾールノボラック型エポキシ樹脂（「エポトートＹＤＣＮ－７０４」、東都化成社製）２１０重量部と、アクリル酸５０重量部と、酢酸１８重量部とを反応させて、エポキシアクリレートを得た。得られたエポキシアクリレート２７８重量部と、テトラヒドロ無水フタル酸４６重量部（エポキシアクリレートの水酸基１．０モルに対して０．３モル）とを反応させ、固形分酸価が５２ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を６５重量％含む溶液を得た。以下、この溶液を（Ａ１）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 1)
In 139 parts by weight of ethyl carbitol acetate, 0.5 part by weight of dimethylbenzylamine as a catalyst and 0.1 part by weight of hydroquinone as a polymerization inhibitor, an epoxy equivalent of 210 and a cresol novolac type epoxy having a softening point of 80 ° C. 210 parts by weight of a resin (“Epototo YDCN-704”, manufactured by Toto Kasei Co., Ltd.), 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid were reacted to obtain an epoxy acrylate. 278 parts by weight of the obtained epoxy acrylate and 46 parts by weight of tetrahydrophthalic anhydride (0.3 mole with respect to 1.0 mole of hydroxyl group of epoxy acrylate) are reacted to form an aromatic ring having a solid content acid value of 52 mgKOH / g. As a result, a solution containing 65% by weight of a carboxyl group-containing resin was obtained. Hereinafter, this solution is referred to as (A1) a carboxyl group-containing resin having an aromatic ring.
　（合成例２）
　温度計、攪拌機、滴下ロート及び還流冷却器を備えたフラスコに、溶剤としてエチルカルビトールアセテートと、触媒としてアゾビスイソブチロニトリルとを入れ、窒素雰囲気下で８０℃に加熱し、メタクリル酸とメチルメタクリレートとスチレンとを３０：５０：２０のモル比で混合したモノマーを２時間かけて滴下した。滴下後、１時間攪拌し、温度を１２０℃に上げた。その後、冷却した。得られた樹脂の全てのモノマー単位の総量のモル量に対するモル比が１０となる量のグリシジルアクリレートを加え、触媒として臭化テトラブチルアンモニウムを用い１００℃で３０時間加熱して、グリシジルアクリレートとカルボキシル基とを付加反応させた。冷却後、フラスコから取り出して、固形分酸価６０ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を５０重量％含む溶液を得た。以下、この溶液を（Ａ２）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 2)
A flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser was charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. under a nitrogen atmosphere, and methacrylic acid and A monomer in which methyl methacrylate and styrene were mixed at a molar ratio of 30:50:20 was added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour, and the temperature was raised to 120 ° C. Then it was cooled. Glycidyl acrylate was added in such an amount that the molar ratio of the total amount of all the monomer units of the obtained resin was 10 and then heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight of a carboxyl group-containing resin having an aromatic ring with a solid content acid value of 60 mgKOH / g. Hereinafter, this solution is referred to as (A2) a carboxyl group-containing resin having an aromatic ring.
　（合成例３）
　温度計、攪拌機、滴下ロート及び還流冷却器を備えたフラスコに、溶剤としてエチルカルビトールアセテートと、触媒としてアゾビスイソブチロニトリルとを入れ、窒素雰囲気下で８０℃に加熱し、メタクリル酸とスチレンとを２０：８０のモル比で混合したモノマーを２時間かけて滴下した。滴下後、１時間攪拌し、温度を１２０℃に上げた。その後、冷却した。冷却後、フラスコから取り出して、固形分酸価６０ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を５０重量％含む溶液を得た。以下、この溶液を（Ａ３）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 3)
A flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser was charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. under a nitrogen atmosphere, and methacrylic acid and A monomer mixed with styrene at a molar ratio of 20:80 was added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour, and the temperature was raised to 120 ° C. Then it was cooled. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight of a carboxyl group-containing resin having an aromatic ring with a solid content acid value of 60 mgKOH / g. Hereinafter, this solution is referred to as (A3) a carboxyl group-containing resin having an aromatic ring.
　（合成例４）
　温度計、攪拌機、滴下ロート及び還流冷却器を備えたフラスコに、溶剤としてエチルカルビトールアセテートと、触媒としてアゾビスイソブチロニトリルとを入れ、窒素雰囲気下で８０℃に加熱し、メタクリル酸とメチルメタクリレートとを３０：７０のモル比で混合したモノマーを２時間かけて滴下した。滴下後、１時間攪拌し、温度を１２０℃に上げた。その後、冷却した。得られた樹脂の全てのモノマー単位の総量のモル量に対するモル比が１０となる量のグリシジルアクリレートを加え、触媒として臭化テトラブチルアンモニウムを用い１００℃で３０時間加熱して、グリシジルアクリレートとカルボキシル基とを付加反応させた。冷却後、フラスコから取り出して、固形分酸価６０ｍｇＫＯＨ／ｇの芳香環を有さないカルボキシル基含有樹脂を５０重量％含む溶液を得た。以下、この溶液を芳香環を有さないカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 4)
A flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser was charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. under a nitrogen atmosphere, and methacrylic acid and A monomer mixed with methyl methacrylate at a molar ratio of 30:70 was added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour, and the temperature was raised to 120 ° C. Then it was cooled. Glycidyl acrylate was added in such an amount that the molar ratio of the total amount of all the monomer units of the obtained resin was 10 and then heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, it was taken out from the flask to obtain a solution containing 50% by weight of a carboxyl group-containing resin having a solid content acid value of 60 mgKOH / g and not having an aromatic ring. Hereinafter, this solution is referred to as a carboxyl group-containing resin having no aromatic ring.
　（合成例５）
　エチルカルビトールアセテート１３９重量部中で、触媒としてジメチルベンジルアミン０．５重量部と、重合禁止剤としてハイドロキノン０．１重量部とを用いて、エポキシ当量２１０、軟化点８０℃のクレゾールノボラック型エポキシ樹脂（「エポトートＹＤＣＮ－７０４」、東都化成社製）２１０重量部とテトラヒドロ無水フタル酸４６重量部（エポキシ基１．０モルに対して０．３モル）とを反応させ、固形分酸価が６７ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を６３重量％含む溶液を得た。以下、この溶液を（Ａ４）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 5)
In 139 parts by weight of ethyl carbitol acetate, 0.5 part by weight of dimethylbenzylamine as a catalyst and 0.1 part by weight of hydroquinone as a polymerization inhibitor, an epoxy equivalent of 210 and a cresol novolac type epoxy having a softening point of 80 ° C. 210 parts by weight of a resin (“Epototo YDCN-704”, manufactured by Toto Kasei Co., Ltd.) and 46 parts by weight of tetrahydrophthalic anhydride (0.3 moles relative to 1.0 mole of epoxy groups) are reacted, and the solid content acid value is A solution containing 63% by weight of a carboxyl group-containing resin having an aromatic ring of 67 mg KOH / g was obtained. Hereinafter, this solution is referred to as (A4) a carboxyl group-containing resin having an aromatic ring.
　（合成例６）
　エチルカルビトールアセテート１３９重量部中で、触媒としてジメチルベンジルアミン０．５重量部と、重合禁止剤としてハイドロキノン０．１重量部とを用いて、エポキシ当量１８０のフェノールノボラック型エポキシ樹脂（「エポトートＹＤＰＮ－６３８」、東都化成社製）１８０重量部と、アクリル酸５０重量部と、酢酸１８重量部とを反応させて、エポキシアクリレートを得た。得られたエポキシアクリレート２４８重量部と、テトラヒドロ無水フタル酸４６重量部（エポキシアクリレートの水酸基１．０モルに対して０．３モル）とを反応させ、固形分酸価が５８ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を６６重量％含む溶液を得た。以下、この溶液を（Ａ５）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 6)
In 139 parts by weight of ethyl carbitol acetate, 0.5 part by weight of dimethylbenzylamine as a catalyst and 0.1 part by weight of hydroquinone as a polymerization inhibitor were used, and a phenol novolac type epoxy resin having an epoxy equivalent of 180 (“Epototo YDPN -638 "(manufactured by Tohto Kasei Co., Ltd.) 180 parts by weight, 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid were reacted to obtain an epoxy acrylate. The resulting 248 parts by weight of epoxy acrylate and 46 parts by weight of tetrahydrophthalic anhydride (0.3 moles relative to 1.0 mole of hydroxyl groups of epoxy acrylate) are reacted to form an aromatic ring having a solid content acid value of 58 mgKOH / g. A solution containing 66% by weight of a carboxyl group-containing resin having was obtained. Hereinafter, this solution is referred to as (A5) a carboxyl group-containing resin having an aromatic ring.
　（合成例７）
　エチルカルビトールアセテート１３９重量部中で、触媒としてジメチルベンジルアミン０．５重量部と、重合禁止剤としてハイドロキノン０．１重量部とを用いて、エポキシ当量１８０のビスフェノールＦ型エポキシ樹脂（「エポトートＹＤＦ－１７０」、東都化成社製）１８０重量部と、アクリル酸５０重量部と、酢酸１８重量部とを反応させて、エポキシアクリレートを得た。得られたエポキシアクリレート２４８重量部と、テトラヒドロ無水フタル酸４６重量部（エポキシアクリレートの水酸基１．０モルに対して０．３モル）とを反応させ、固形分酸価が５８ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を６６重量％含む溶液を得た。以下、この溶液を（Ａ６）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 7)
In 139 parts by weight of ethyl carbitol acetate, 0.5 parts by weight of dimethylbenzylamine as a catalyst and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were used, and a bisphenol F type epoxy resin having an epoxy equivalent of 180 (“Epototo YDF -170 "(manufactured by Tohto Kasei Co., Ltd.) 180 parts by weight, 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid were reacted to obtain an epoxy acrylate. The resulting 248 parts by weight of epoxy acrylate and 46 parts by weight of tetrahydrophthalic anhydride (0.3 moles relative to 1.0 mole of hydroxyl groups of epoxy acrylate) are reacted to form an aromatic ring having a solid content acid value of 58 mgKOH / g. A solution containing 66% by weight of a carboxyl group-containing resin having was obtained. Hereinafter, this solution is referred to as (A6) a carboxyl group-containing resin having an aromatic ring.
　（合成例８）
　エチルカルビトールアセテート１３９重量部中で、触媒としてジメチルベンジルアミン０．５重量部と、重合禁止剤としてハイドロキノン０．１重量部とを用いて、エポキシ当量１８０のビスフェノールＡ型エポキシ樹脂（「エポトートＹＤ－１２７」、東都化成社製）１８０重量部と、アクリル酸５０重量部と、酢酸１８重量部とを反応させて、エポキシアクリレートを得た。得られたエポキシアクリレート２４８重量部と、テトラヒドロ無水フタル酸４６重量部（エポキシアクリレートの水酸基１．０モルに対して０．３モル）とを反応させ、固形分酸価が５８ｍｇＫＯＨ／ｇの芳香環を有するカルボキシル基含有樹脂を６６重量％含む溶液を得た。以下、この溶液を（Ａ７）芳香環を有するカルボキシル基含有樹脂と呼ぶ。 (Synthesis Example 8)
In 139 parts by weight of ethyl carbitol acetate, 0.5 part by weight of dimethylbenzylamine as a catalyst and 0.1 part by weight of hydroquinone as a polymerization inhibitor were used, and a bisphenol A type epoxy resin having an epoxy equivalent of 180 (“Epototo YD -127 "(manufactured by Tohto Kasei Co., Ltd.) 180 parts by weight, 50 parts by weight of acrylic acid and 18 parts by weight of acetic acid were reacted to obtain an epoxy acrylate. The resulting 248 parts by weight of epoxy acrylate and 46 parts by weight of tetrahydrophthalic anhydride (0.3 moles relative to 1.0 mole of hydroxyl groups of epoxy acrylate) are reacted to form an aromatic ring having a solid content acid value of 58 mgKOH / g. A solution containing 66% by weight of a carboxyl group-containing resin having was obtained. Hereinafter, this solution is referred to as (A7) a carboxyl group-containing resin having an aromatic ring.
　（Ｂ）酸化チタン
　以下の実施例及び比較例で用いた酸化チタンの詳細は以下の通りである。
　ルチル型酸化チタン（１）：石原産業社製、型番：ＣＲ－９７。塩素法により製造されたルチル型酸化チタン。
　ルチル型酸化チタン（２）：石原産業社製、型番：ＣＲ－５０。塩素法により製造されたルチル型酸化チタン。
　ルチル型酸化チタン（３）：石原産業社製、型番：ＣＲ－９０。塩素法により製造されたルチル型酸化チタン、シリカにより処理されている。
　ルチル硫酸法酸化チタン（１）：硫酸法により製造されたルチル酸化チタン、石原産業社製、品番：Ｒ－６３０。
　ルチル硫酸法酸化チタン（２）：硫酸法によって製造されたルチル型酸化チタン、石原産業社製、品番：Ｒ－５５０。シリカにより処理されている。
　アナターゼ型酸化チタン：石原産業社製、品番：Ａ－２２０。 (B) Titanium oxide Details of titanium oxide used in the following examples and comparative examples are as follows.
Rutile type titanium oxide (1): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-97. Rutile-type titanium oxide produced by the chlorine method.
Rutile type titanium oxide (2): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-50. Rutile-type titanium oxide produced by the chlorine method.
Rutile type titanium oxide (3): manufactured by Ishihara Sangyo Co., Ltd., model number: CR-90. It is treated with rutile titanium oxide and silica produced by the chlorine method.
Rutile sulfuric acid method titanium oxide (1): Rutile titanium oxide produced by the sulfuric acid method, manufactured by Ishihara Sangyo Co., Ltd., product number: R-630.
Rutile sulfuric acid method titanium oxide (2): Rutile type titanium oxide produced by the sulfuric acid method, manufactured by Ishihara Sangyo Co., Ltd., product number: R-550. Treated with silica.
Anatase type titanium oxide: manufactured by Ishihara Sangyo Co., Ltd., product number: A-220.
　（他の成分）
　後述の実施例及び比較例では、下記の表１，２に示す成分を適宜用いた。 (Other ingredients)
In Examples and Comparative Examples described later, the components shown in Tables 1 and 2 below were appropriately used.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（実施例１）
　合成例１で得られた芳香環を有するカルボキシル基含有樹脂（Ａ１）２５重量部と、ルチル型塩素法酸化チタン（石原産業社製「ＣＲ－９７」）４０重量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製「ｊＥＲ８２８」）８重量部と、光重合開始剤（光ラジカル発生剤、ＢＡＳＦジャパン社製「ＴＰＯ」）２重量部と、フェノール系酸化防止剤（チバジャパン社製「ＩＲＧＡＮＯＸ　１０１０」）０．５重量部と、希釈剤としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ、ダイセルサイテック社製）５重量部と、エチルカルビトールアセテート（ダイセル化学工業社製）２０重量部とを配合し、混合機（練太郎ＳＰ－５００、シンキー社製）にて３分間混合した後、３本ロールにて混合し、混合物を得た。その後、ＳＰ－５００を用いて、得られた混合物を３分間脱泡することにより、感光性組成物を得た。 Example 1
25 parts by weight of the carboxyl group-containing resin (A1) having an aromatic ring obtained in Synthesis Example 1, 40 parts by weight of a rutile type chlorine method titanium oxide (“CR-97” manufactured by Ishihara Sangyo Co., Ltd.), and a bisphenol A type epoxy resin ("JER828" manufactured by Japan Epoxy Resin Co., Ltd.) 8 parts by weight, 2 parts by weight of photopolymerization initiator (photo radical generator, "TPO" manufactured by BASF Japan), and phenolic antioxidant ("IRGANOX" manufactured by Ciba Japan) 1010 ") 0.5 parts by weight, 5 parts by weight of dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel Cytec) as a diluent, and 20 parts by weight of ethyl carbitol acetate (manufactured by Daicel Chemical Industries), After mixing for 3 minutes with a mixer (Nertaro SP-500, manufactured by Shinky Corp.), the mixture was mixed with 3 rolls to obtain a mixture. Thereafter, the resulting mixture was degassed for 3 minutes using SP-500 to obtain a photosensitive composition.
　（実施例２～２３及び比較例１～５）
　使用した材料の種類及び配合量を下記の表３～６に示すように変更したこと以外は、実施例１と同様にして、感光性組成物を得た。 (Examples 2 to 23 and Comparative Examples 1 to 5)
A photosensitive composition was obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Tables 3 to 6 below.
　（実施例１～２３及び比較例１～５の評価）
　（１）測定サンプルの調製
　１００ｍｍ×１００ｍｍ×厚さ０．８ｍｍのＦＲ－４である基板を用意した。この基板上に、スクリーン印刷法により、１００メッシュのポリエステルバイアス製の版を用いて、ベタパターンで感光性組成物を印刷した。印刷後、８０℃のオーブン内で２０分間乾燥させ、レジスト材料層を基板上に形成した。次に、所定のパターンを有するフォトマスクを介して、紫外線照射装置を用い、レジスト材料層に波長３６５ｎｍの紫外線を、照射エネルギーが４００ｍＪ／ｃｍ２となるように１００ｍＷ／ｃｍ２の紫外線照度で４秒間照射した。その後、未露光部のレジスト材料層を除去してパターンを形成するために、炭酸ナトリウムの１重量％水溶液にレジスト材料層を浸漬して現像し、基板上にレジスト膜を形成した。その後、１５０℃のオーブン内で１時間加熱して、レジスト膜を後硬化させることにより、測定サンプルとしてのレジスト膜を得た。得られたレジスト膜の厚みは２０μｍであった。 (Evaluation of Examples 1 to 23 and Comparative Examples 1 to 5)
(1) Preparation of measurement sample A substrate of FR-4 having a size of 100 mm × 100 mm × thickness 0.8 mm was prepared. On this board | substrate, the photosensitive composition was printed by the solid pattern using the plate made from a 100 mesh polyester bias by the screen printing method. After printing, it was dried in an oven at 80 ° C. for 20 minutes to form a resist material layer on the substrate. Next, using a UV irradiation device through a photomask having a predetermined pattern, UV light having a wavelength of 365 nm is applied to the resist material layer at a UV intensity of 100 mW / cm 2 so that the irradiation energy is 400 mJ / cm 2. Irradiated for 2 seconds. Thereafter, in order to remove the resist material layer in the unexposed area and form a pattern, the resist material layer was dipped in a 1% by weight aqueous solution of sodium carbonate and developed to form a resist film on the substrate. Thereafter, the resist film was post-cured by heating in an oven at 150 ° C. for 1 hour to obtain a resist film as a measurement sample. The thickness of the obtained resist film was 20 μm.
　（２）耐熱黄変性
　測定サンプルを加熱オーブン内に入れ、２７０℃で５分間加熱した。 (2) Heat-resistant yellowing The measurement sample was put in a heating oven and heated at 270 ° C. for 5 minutes.
　色彩・色差計（コニカミノルタ社製、ＣＲ－４００）を用いて、熱処理される前の評価サンプルのＬ＊、ａ＊、ｂ＊を測定した。また、熱処理された後の評価サンプルのＬ＊、ａ＊、ｂ＊を測定し、これら２つの測定値からΔＥ＊ａｂを求めた。下記の判定基準で耐熱黄変性を判定した。 Using a color / color difference meter (CR-400, manufactured by Konica Minolta Co., Ltd.), L *, a *, and b * of the evaluation sample before heat treatment were measured. Further, L *, a *, and b * of the evaluation sample after the heat treatment were measured, and ΔE * ab was obtained from these two measured values. Heat-resistant yellowing was determined according to the following criteria.
　［耐熱黄変性の判定基準］
　○○：熱処理の後の評価サンプルのΔＥ＊ａｂが２．５未満
　○：熱処理の後の評価サンプルのΔＥ＊ａｂが２．５以上、４未満
　△：熱処理の後の評価サンプルのΔＥ＊ａｂが４以上、５．５未満
　×：熱処理の後の評価サンプルのΔＥ＊ａｂが５．５以上 [Criteria for heat-resistant yellowing]
◯: ΔE * ab of the evaluation sample after heat treatment is less than 2.5 ○: ΔE * ab of the evaluation sample after heat treatment is 2.5 or more and less than 4 Δ: ΔE * ab of the evaluation sample after heat treatment Is 4 or more and less than 5.5 ×: ΔE * ab of the evaluation sample after the heat treatment is 5.5 or more
　（３）耐熱クラック性
　測定サンプルを加熱オーブン内に入れ、２７０℃で５分間加熱した。熱処理された後の評価サンプルのクラックの有無を、顕微鏡を用いずに確認した。さらに、熱処理された後の評価サンプルのクラックの有無を、顕微鏡を用いて確認した。下記の判定基準で耐熱クラック性を判定した。 (3) Thermal crack resistance The measurement sample was put in a heating oven and heated at 270 ° C. for 5 minutes. The presence or absence of cracks in the evaluation sample after the heat treatment was confirmed without using a microscope. Furthermore, the presence or absence of the crack of the evaluation sample after heat processing was confirmed using the microscope. The heat crack resistance was determined according to the following criteria.
　［耐熱クラック性の判定基準］
　○○：顕微鏡を用いずに見ても、顕微鏡で見ても、クラックが確認できない
　○：顕微鏡を用いずに見るとクラックが確認できないものの、顕微鏡を用いて見るとクラックが確認できる
　×：顕微鏡を用いずに見ても、クラックが確認できる
　××：顕微鏡を用いずに見ても、クラックが確認でき、かつレジスト膜の剥離が確認できる
　結果を下記の表３～６に示す。なお、評価欄に、前述した式（１）の「（５Ｖ＋３Ｗ）／（３Ｘ１＋Ｘ２＋１００Ｙ）」の値を併せて示す。 [Criteria for heat-resistant crack resistance]
○○: Cracks cannot be confirmed even when viewed without using a microscope or with a microscope ○: Cracks cannot be confirmed when viewed without using a microscope, but cracks can be confirmed when viewed with a microscope ×: Microscope Cracks can be confirmed even without using XX: Cracks can be confirmed and peeling of the resist film can be confirmed without using a microscope. Tables 3 to 6 show the results. In the evaluation column, the value of “(5V + 3W) / (3X1 + X2 + 100Y)” in the above-described formula (1) is also shown.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　次に、第１の液と第２の液とを有する２液混合型の感光性組成物を用意した。 Next, a two-component mixed photosensitive composition having a first liquid and a second liquid was prepared.
　（実施例２４）
　下記の表７に示す材料を下記の表７に示す配合量で配合し、混合機（練太郎ＳＰ－５００、シンキー社製）にて３分間混合した後、３本ロールにて混合し、混合物を得た。その後、ＳＰ－５００を用いて、得られた混合物を３分間脱泡することにより、第１の液を得た。 (Example 24)
The materials shown in Table 7 below are blended in the amounts shown in Table 7 below, mixed for 3 minutes with a mixer (Nertaro SP-500, manufactured by Shinky Corp.), then mixed with 3 rolls, and the mixture Got. Thereafter, the obtained mixture was degassed for 3 minutes using SP-500 to obtain a first liquid.
　下記の表７に示す材料を下記の表７に示す配合量で配合し、混合機（練太郎ＳＰ－５００、シンキー社製）にて３分間混合した後、３本ロールにて混合し、混合物を得た。その後、ＳＰ－５００を用いて、得られた混合物を３分間脱泡することにより、第２の液を得た。 The materials shown in Table 7 below are blended in the amounts shown in Table 7 below, mixed for 3 minutes with a mixer (Nertaro SP-500, manufactured by Shinky Corp.), then mixed with 3 rolls, and the mixture Got. Thereafter, using SP-500, the resulting mixture was degassed for 3 minutes to obtain a second liquid.
　上記のようにして、第１，第２の液を有する２液混合型の感光性組成物を用意した。 As described above, a two-component mixed photosensitive composition having the first and second solutions was prepared.
　（実施例２５～３５）
　第１の液及び第２の液で使用した材料の種類及び配合量を下記の表７，８に示すように変更したこと以外は、実施例２４と同様にして、２液混合型の感光性組成物を得た。 (Examples 25 to 35)
Two-component mixed type photosensitivity in the same manner as in Example 24, except that the types and amounts of materials used in the first and second liquids were changed as shown in Tables 7 and 8 below. A composition was obtained.
　（実施例２５～３５の評価）
　実施例１～２４及び比較例１～５と同様の評価を実施した。なお、基板上に感光性組成物を印刷する際に、第１，第２の液を混合した。 (Evaluation of Examples 25 to 35)
Evaluations similar to those in Examples 1 to 24 and Comparative Examples 1 to 5 were performed. In addition, when printing the photosensitive composition on a board | substrate, the 1st, 2nd liquid was mixed.
　結果を下記の表７，８に示す。 Results are shown in Tables 7 and 8 below.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　１…ＬＥＤデバイス
　２…基板
　２ａ…上面
　３…ソルダーレジスト膜
　３ａ，３ｂ…開口部
　４ａ，４ｂ…電極
　５…ガラス層
　６…樹脂層
　７…ＬＥＤチップ
　７ａ…下面
　８ａ，８ｂ…端子
　９ａ，９ｂ…半田 DESCRIPTION OF SYMBOLS 1 ... LED device 2 ... Board | substrate 2a ... Upper surface 3 ... Solder resist film 3a, 3b ... Opening part 4a, 4b ... Electrode 5 ... Glass layer 6 ... Resin layer 7 ... LED chip 7a ... Lower surface 8a, 8b ... Terminal 9a, 9b ... solder

Claims (13)

  1. 　芳香環を有するカルボキシル基含有樹脂と、酸化チタンと、環状エーテル骨格を有する化合物と、光重合開始剤とを含む、感光性組成物。 A photosensitive composition comprising a carboxyl group-containing resin having an aromatic ring, titanium oxide, a compound having a cyclic ether skeleton, and a photopolymerization initiator.
  2. 　前記芳香環を有するカルボキシル基含有樹脂が、不飽和二重結合を有する、請求項１に記載の感光性組成物。 The photosensitive composition according to claim 1, wherein the carboxyl group-containing resin having an aromatic ring has an unsaturated double bond.
  3. 　前記芳香環を有するカルボキシル基含有樹脂が、芳香環を有するエポキシ化合物と多塩基酸化合物とを反応させて得られる樹脂、又は芳香環を有するエポキシ化合物と不飽和二重結合を少なくとも１つ有するカルボキシル基含有化合物とを反応させた後、多塩基酸化合物をさらに反応させて得られる樹脂である、請求項１又は２に記載の感光性組成物。 The carboxyl group-containing resin having an aromatic ring is a resin obtained by reacting an epoxy compound having an aromatic ring with a polybasic acid compound, or a carboxyl having at least one unsaturated double bond with an epoxy compound having an aromatic ring The photosensitive composition of Claim 1 or 2 which is resin obtained by making a polybasic acid compound react further, after making it react with a group containing compound.
  4. 　前記芳香環を有するカルボキシル基含有樹脂が、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有する、請求項１～３に記載の感光性組成物。 The carboxyl group-containing resin having an aromatic ring is at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. The photosensitive composition according to claim 1, which has one structural unit.
  5. 　前記環状エーテル骨格を有する化合物が芳香環を有する、請求項１～４のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 4, wherein the compound having a cyclic ether skeleton has an aromatic ring.
  6. 　前記酸化チタンがルチル型酸化チタンである、請求項１～５のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 5, wherein the titanium oxide is a rutile type titanium oxide.
  7. 　前記酸化チタンが、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含む、請求項１～６のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 6, wherein the titanium oxide comprises rutile titanium oxide surface-treated with silicon oxide or a silicone compound.
  8. 　酸化防止剤をさらに含む、請求項１～７のいずれか１項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 7, further comprising an antioxidant.
  9. 　前記酸化防止剤がフェノール系酸化防止剤である、請求項８に記載の感光性組成物。 The photosensitive composition according to claim 8, wherein the antioxidant is a phenolic antioxidant.
  10. 　フェノール系酸化防止剤を含まないか、又はフェノール系酸化防止剤をさらに含み、
    　上記芳香環を有するカルボキシル基含有樹脂が、メチレン基を介して２つの芳香環が結合した第１の構造単位、及びオキシメチレン基と芳香環とがエーテル結合した第２の構造単位の内の少なくとも１つの構造単位を有し、
    　前記酸化チタンが、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含まないか、又は該ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含み、
    　前記芳香環を有するカルボキシル基含有樹脂の前記第１の構造単位のモル数をＶとし、前記芳香環を有するカルボキシル基含有樹脂の前記第２の構造単位のモル数をＷとし、前記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンのモル数をＸ１とし、前記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンではない酸化チタンのモル数をＸ２とし、かつ前記フェノール系酸化防止剤のフェノール基のモル数をＹとしたときに、下記式（１）を満たす、請求項１～９のいずれか１項に記載の感光性組成物。
    　０．０６≦（５Ｖ＋３Ｗ）／（３Ｘ１＋Ｘ２＋１００Ｙ）≦０．３５　・・・式（１）     Does not contain a phenolic antioxidant, or further contains a phenolic antioxidant,
    The carboxyl group-containing resin having an aromatic ring is at least one of a first structural unit in which two aromatic rings are bonded via a methylene group, and a second structural unit in which an oxymethylene group and an aromatic ring are ether-bonded. Having one structural unit,
    The titanium oxide does not include a rutile type titanium oxide surface-treated with a silicon oxide or a silicone compound, or includes a rutile type titanium oxide surface-treated with the silicon oxide or a silicone compound,
    The number of moles of the first structural unit of the carboxyl group-containing resin having an aromatic ring is V, the number of moles of the second structural unit of the carboxyl group-containing resin having an aromatic ring is W, and the silicon oxide Alternatively, the number of moles of rutile titanium oxide surface-treated with a silicone compound is X1, the number of moles of titanium oxide that is not the rutile titanium oxide surface-treated with the silicon oxide or silicone compound is X2, and the phenol type The photosensitive composition according to any one of claims 1 to 9, which satisfies the following formula (1), where Y is the number of moles of phenol groups in the antioxidant.
    0.06 ≦ (5V + 3W) / (3X1 + X2 + 100Y) ≦ 0.35 Expression (1)
  11. 　第１の液と、第２の液とを有し、該第１，第２の液が混合されて用いられる２液混合型の感光性組成物であり、
    　前記芳香環を有するカルボキシル基含有樹脂と、前記酸化チタンと、前記環状エーテル骨格を有する化合物と、前記光重合開始剤とはそれぞれ、前記第１の液及び前記第２の液の内の少なくとも一方に含まれており、
    　前記第１，第２の液が混合された混合物が、前記芳香環を有するカルボキシル基含有樹脂と、前記酸化チタンと、前記環状エーテル骨格を有する化合物と、前記光重合開始剤とを含む、請求項１～１０のいずれか１項に記載の感光性組成物。     A two-component mixed photosensitive composition that has a first liquid and a second liquid and is used by mixing the first and second liquids.
    The carboxyl group-containing resin having an aromatic ring, the titanium oxide, the compound having the cyclic ether skeleton, and the photopolymerization initiator are each at least one of the first liquid and the second liquid. Included in the
    The mixture in which the first and second liquids are mixed contains the carboxyl group-containing resin having the aromatic ring, the titanium oxide, the compound having the cyclic ether skeleton, and the photopolymerization initiator. Item 11. The photosensitive composition according to any one of items 1 to 10.
  12. 　前記第１の液が、前記芳香環を有するカルボキシル基含有樹脂を少なくとも含み、かつ、前記第２の液が、前記環状エーテル骨格を有する化合物を少なくとも含む、請求項１１に記載の感光性組成物。 The photosensitive composition according to claim 11, wherein the first liquid includes at least a carboxyl group-containing resin having the aromatic ring, and the second liquid includes at least a compound having the cyclic ether skeleton. .
  13. 　回路を表面に有するプリント配線板本体と、
    　前記プリント配線板本体の前記回路が設けられた表面に積層されたレジスト膜とを備え、
    　前記レジスト膜が、請求項１～１２のいずれか１項に記載の感光性組成物を用いて形成されている、プリント配線板。     A printed wiring board body having a circuit on its surface;
    A resist film laminated on the surface of the printed wiring board body on which the circuit is provided;
    A printed wiring board, wherein the resist film is formed using the photosensitive composition according to any one of claims 1 to 12.
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JP4891434B2 (en) 2012-03-07
TW201109841A (en) 2011-03-16

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