WO2012111356A1 - Two-liquid mixing first and second liquids and method for producing printed circuit board - Google Patents

Two-liquid mixing first and second liquids and method for producing printed circuit board Download PDF

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Publication number
WO2012111356A1
WO2012111356A1 PCT/JP2012/050105 JP2012050105W WO2012111356A1 WO 2012111356 A1 WO2012111356 A1 WO 2012111356A1 JP 2012050105 W JP2012050105 W JP 2012050105W WO 2012111356 A1 WO2012111356 A1 WO 2012111356A1
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Prior art keywords
liquid
distillation properties
organic solvent
naphtha
group
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PCT/JP2012/050105
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French (fr)
Japanese (ja)
Inventor
秀 中村
上田　倫久
崇至 鹿毛
駿夫 ▲高▼橋
貴志 渡邉
Original Assignee
積水化学工業株式会社
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Priority claimed from JP2011092713A external-priority patent/JP4850313B1/en
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 CN201280000309.XA priority Critical patent/CN102762627B/en
Priority to KR1020127016064A priority patent/KR101250736B1/en
Publication of WO2012111356A1 publication Critical patent/WO2012111356A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector

Definitions

  • the present invention relates to a two-component mixed type first and second solution for obtaining a photosensitive composition as a mixture.
  • the present invention is a two-liquid mixture suitably used for forming a solder resist film on a substrate or forming a resist film that reflects light on a substrate on which a light emitting diode chip is mounted.
  • the present invention relates to a method for manufacturing a printed wiring board using first and second liquids of a mold and the first and second liquids of the two liquid mixture type.
  • Solder resist films are widely used as protective films for protecting printed wiring boards from high-temperature solder.
  • 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 material 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 material containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, a rutile titanium oxide, and a diluent. Yes.
  • An object of the present invention is a two-liquid mixed type first and second liquid, which is excellent in the mixing property of the first and second liquids, and is a mixture in which the first and second liquids are mixed.
  • the two-liquid mixed type first and second liquids that can be uniformly coated while suppressing unevenness, and the two-liquid mixing It is to provide a method for manufacturing a printed wiring board using first and second liquids of a mold.
  • the two-liquid mixed type first and second liquids for obtaining a photosensitive composition which is a mixture
  • the two-liquid mixed type first and second liquids are The photosensitive composition which is a liquid before the first and second liquids are mixed, and is a mixture in which the first and second liquids are mixed, and a polymerizable polymer having a carboxyl group as a whole
  • a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent wherein the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and distillation properties as the organic solvent.
  • the second liquid contains a compound having the cyclic ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the initial boiling point in the distillation property is 150. At least one selected from the group consisting of naphtha having an endpoint in distillation properties of 220 ° C. or lower, and the first liquid contains the photopolymerization initiator or the titanium oxide, Or both the photopolymerization initiator and the titanium oxide And when the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, A two-liquid mixed type first and second liquid containing two titanium oxides are provided.
  • a method of manufacturing a printed wiring board according to the present invention is a manufacturing of a printed wiring board including a printed wiring board main body having a circuit on the surface and a solder resist film laminated on the surface of the printed wiring board main body provided with the circuit.
  • a photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed, is applied onto the surface of the main body provided with the circuit, and the circuit of the printed wiring board main body is provided.
  • the photosensitive composition which is a solder resist composition in which the first and second liquids are mixed, has a polymerizable weight having a carboxyl group as a whole.
  • Coalescence A photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent, wherein the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and distillation as the organic solvent.
  • the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and distillation as the organic solvent.
  • the first liquid includes the polymerizable polymer
  • the organic solvent As part of the organic solvent, at least selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less. 1 type is included
  • the second liquid is the ring Including a compound having an ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point in distillation properties of 150 ° C. or higher, and an end point in distillation properties of 220 ° C. or lower.
  • the first liquid contains the photopolymerization initiator, the titanium oxide, or the photopolymerization initiator and the titanium oxide.
  • the second liquid contains the photopolymerization initiator, and the first liquid does not contain the titanium oxide.
  • the second liquid contains the titanium oxide.
  • the first liquid may be used as a part of the organic solvent. It includes at least two selected from the group consisting of propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less.
  • the first liquid is a part of the organic solvent, Dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate at least, or diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties Including at least.
  • the first liquid is a part of the organic solvent, It contains at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
  • the photosensitive composition contains dipropylene glycol as the organic solvent.
  • a naphtha having an initial distillation point in the distillation property of 150 ° C. or more and an end point in the distillation property of 290 ° C. or less is a naphtha having an initial distillation point in the distillation property of 150 ° C. or more and an end point in the distillation property of 220 ° C. or less.
  • the first liquid contains the photopolymerization initiator.
  • the first liquid contains the titanium oxide.
  • the first liquid includes the photopolymerization initiator and the oxidation. Including both titanium.
  • the photosensitive composition in which the first and second liquids are mixed is suitably used as the solder resist composition.
  • the photosensitive composition in which the first and second liquids are mixed is preferably a solder resist composition.
  • the two-liquid mixed type first and second liquids according to the present invention are two-liquid mixed type first and second liquids for obtaining a photosensitive composition as a mixture.
  • the first and second liquids are liquids before the first and second liquids are mixed, and the photosensitive composition, which is a mixture of the first and second liquids, is a carboxyl group as a whole.
  • the first liquid is the polymerizable polymer Including and As part of the organic solvent, at least selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less.
  • the second liquid contains the compound having the cyclic ether group and, as a part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the initial boiling point in distillation properties are Whether the first liquid contains the photopolymerization initiator or the titanium oxide, including at least one selected from the group consisting of naphtha having a distillation property of 150 ° C. or higher and an end point in distillation property of 220 ° C. or lower. Or the photopolymerization initiator and the titanium oxide Therefore, when the photosensitive composition after mixing is coated on the coating target member, the coating is uniformly performed while suppressing unevenness. can do.
  • FIG. 1 is a partially cutaway front sectional view schematically showing an example of an LED device having a resist film using a two-liquid mixed type first and second liquid according to an embodiment of the present invention.
  • the two-liquid mixed type first and second liquids according to the present invention are used to obtain a photosensitive composition which is a mixture.
  • the two-liquid mixed type first and second liquids according to the present invention are kits used for obtaining a photosensitive composition as a mixture.
  • the two-liquid mixed type first and second liquids according to the present invention are mixed and used.
  • the two-liquid mixed type first and second liquids according to the present invention are liquids before the first and second liquids are mixed.
  • the first and second liquids before being mixed are the photosensitive compositions before being mixed.
  • the photosensitive composition which is a mixture in which the first and second liquids of the two liquid mixture type according to the present invention are mixed as a whole is a polymerizable polymer (A) having a carboxyl group and a photopolymerization initiator (B ), A compound (C) having a cyclic ether group, titanium oxide (D), and an organic solvent (E) (hereinafter, the organic solvent contained in the entire photosensitive composition is referred to as an organic solvent (E). May be included).
  • the mixture in which the first and second liquids are mixed is a photosensitive composition, and the mixed photosensitive composition as a whole is a polymerizable polymer (A) having a carboxyl group and a photopolymerization initiator.
  • B the compound (C) which has a cyclic ether group, a titanium oxide (D), and the organic solvent (E) are included.
  • the photosensitive composition includes, as the organic solvent (E), dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and 290 ° C. or lower in distillation properties. At least two selected from the group consisting of:
  • the first liquid contains the polymerizable polymer (A) and, as a part of the organic solvent (E), dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and an initial boiling point of 150 in distillation properties are 150. It contains at least one selected from the group consisting of naphtha having an end point in the distillation property of 290 ° C. or lower.
  • the second liquid contains the compound (C) having the cyclic ether group, and as part of the organic solvent (E), diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial distillation in distillation properties. It includes at least one selected from the group consisting of naphtha having a point of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower.
  • the first liquid contains the photopolymerization initiator (B), contains the titanium oxide (D), or contains both the photopolymerization initiator (B) and the titanium oxide (D). .
  • the second liquid contains the photopolymerization initiator (B).
  • the first liquid does not contain the titanium oxide (D)
  • the second liquid contains the titanium oxide (D).
  • the photopolymerization initiator (B) and the titanium oxide (D) may each be contained in the first liquid, may be contained in the second liquid, the first liquid, and the second liquid It may be contained in both of the liquid.
  • the two-liquid mixed type first and second liquids according to the present invention contain a polymerizable monomer described later or an antioxidant described later
  • the polymerizable monomer And the antioxidant may be contained in the first liquid, may be contained in the second liquid, or may be contained in both the first liquid and the second liquid.
  • the mixing properties of the first and second liquids can be enhanced. Furthermore, when the photosensitive composition after mixing is applied onto a coating target member such as a substrate, it can be uniformly applied while suppressing unevenness caused largely by titanium oxide. In particular, when the photosensitive composition after mixing is applied by screen printing, streaky unevenness can be suppressed.
  • the two-liquid mixed type first and second liquids according to the present invention are preferably two-liquid mixed type first and second liquids to be applied by screen printing.
  • the photopolymerization initiator (B) is contained in the first liquid, not the second liquid. In this case, the mixing properties of the first and second liquids are further enhanced, and the photosensitive composition can be applied more uniformly.
  • the titanium oxide (D) is preferably contained in the first liquid, not the second liquid. In this case, the dispersibility of titanium oxide (D) is increased, the mixing properties of the first and second liquids are further increased, and the photosensitive composition can be applied more uniformly.
  • both the photopolymerization initiator (B) and the titanium oxide (D) are contained in the first liquid instead of the second liquid.
  • the dispersibility of titanium oxide (D) is further enhanced, the mixing properties of the first and second liquids are further enhanced, and the photosensitive composition can be applied more uniformly.
  • the polymerizable polymer (A) has a carboxyl group.
  • the polymerizable polymer (A) having a carboxyl group has polymerizability and can be polymerized. When the polymerizable polymer (A) has a carboxyl group, the developability of the photosensitive composition is improved.
  • Examples of the polymerizable polymer (A) include an acrylic resin having a carboxyl group, an epoxy resin having a carboxyl group, and an olefin resin having a carboxyl group.
  • the “resin” is not limited to a solid resin, and includes a liquid resin and an oligomer.
  • the polymerizable polymer (A) is preferably the following carboxyl group-containing resins (a) to (e).
  • (E) A resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or an epoxy compound having an aromatic ring and at least one unsaturated double bond Resin obtained by further reacting with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride after reacting with a carboxyl group-containing compound Polymerization having the carboxyl group in 100% by weight of the photosensitive composition
  • the content of the polymer (A) is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less.
  • Photopolymerization initiator (B) Since the said photosensitive composition contains a photoinitiator (B), a photosensitive composition can be hardened by irradiation of light.
  • the photopolymerization initiator (B) is not particularly limited. As for a photoinitiator (B), only 1 type may be used and 2 or more types may be used together.
  • Examples of the photopolymerization initiator (B) include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, benzoic acid ester , Acridine, phenazine, titanocene, ⁇ -aminoalkylphenone, oxime, and derivatives thereof.
  • the said photoinitiator (B) only 1 type may be used and 2 or more types may be used together.
  • the content of the photopolymerization initiator (B) is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. 30 parts by weight or less, more preferably 15 parts by weight or less.
  • the photosensitivity of the photosensitive composition can be further enhanced.
  • the photosensitive composition contains a compound (C) having a cyclic ether skeleton. Further, the use of the compound (C) having the cyclic ether skeleton also improves the curability of the photosensitive composition.
  • Examples of the compound (C) 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, tetra Glycidyl xylenoyl ethane 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 novolak type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene resin Norick type epoxy resins, silicone-modified epoxy resin and ⁇ - caprolactone-modified epoxy resin. Only 1 type may be used for the compound (C) which has the said cyclic ether ske
  • the compound (C) having the cyclic ether skeleton reacts with the carboxyl group of the polymerizable polymer (A) having the carboxyl group to act to cure the photosensitive composition.
  • the content of the compound (C) having a cyclic ether skeleton is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less.
  • the content of the compound (C) having the cyclic ether skeleton is not less than the above lower limit and not more than the above upper limit, the electrical insulation of the resist film can be further enhanced.
  • titanium oxide (D) Since the said photosensitive composition contains titanium oxide (D), hardened
  • the titanium oxide (D) contained in the said photosensitive composition is not specifically limited. As for titanium oxide (D), only 1 type may be used and 2 or more types may be used together.
  • titanium oxide (D) By using the above titanium oxide (D), it is possible to form a resist film having a high reflectance as compared with the case where an inorganic filler other than titanium oxide (D) is used.
  • the titanium oxide (D) 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 (D) preferably contains rutile titanium oxide that has been 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 preferably 10% by weight or more, more preferably 30% by weight or more and 100% by weight or less. It is.
  • the total amount of the titanium oxide (D) may be rutile titanium oxide surface-treated with the silicon oxide or the silicone compound.
  • rutile titanium oxide surface-treated with silicon oxide or silicone compound examples include, for example, product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile chlorine method titanium oxide, and manufactured by Ishihara Sangyo Co., Ltd., which is a rutile sulfuric acid method titanium oxide.
  • the content of titanium oxide (D) is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, preferably 80% by weight or less. More preferably, it is 75 weight% or less, More preferably, it is 70 weight% or less.
  • the content of titanium oxide (D) is not less than the above lower limit and not more than the above upper limit, the resist film is hardly yellowed when exposed to high temperatures. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.
  • the photosensitive composition contains an organic solvent (E).
  • the photosensitive composition in which the first and second liquids are mixed contains an organic solvent (E).
  • the photosensitive composition contains at least two organic solvents.
  • the organic solvent (E1) contained in the first liquid hereinafter, the organic solvent contained in the first liquid may be referred to as an organic solvent (E1)
  • the second liquid Is different from the organic solvent (E2) contained in the organic solvent (hereinafter, the organic solvent contained in the second liquid may be referred to as the organic solvent (E2)).
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butyl Carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, glycol ethers such as 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, diethylene glycol monoethyl ester Ether acetate, dipropylene glycol monomethyl ether acetate, esters such
  • the first liquid is distilled as a part of the organic solvent (E) with dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and an initial boiling point of 150 ° C. or more in distillation properties. At least one selected from the group consisting of naphtha whose end point in properties is 290 ° C. or lower is essential. At least one of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties is an organic solvent (E1).
  • the second liquid has diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point of 150 ° C. as a part of the organic solvent (E).
  • at least 1 sort (s) selected from the group which consists of naphtha whose end point in distillation property is 220 degrees C or less is included.
  • At least one selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and naphtha having an initial distillation point of 150 ° C. or more in distillation properties and an end point of distillation properties of 220 ° C. or less is an organic solvent ( E2).
  • ⁇ / RTI> By including such organic solvents (E1) and (E2) in the first and second liquids, the mixing properties of the first and second liquids are remarkably improved.
  • the use of the specific organic solvent (E1) or (E2) further includes the specific organic solvent (E1) or (E2) separately in the first liquid and the second liquid. This greatly contributes to the improvement of the mixing properties of the first and second liquids and the suppression of unevenness after the application of the mixed photosensitive composition.
  • the “initial boiling point in distillation properties” and the “end point in distillation properties” mean values measured by JIS K2254 “Petroleum products—distillation test method”.
  • the first liquid is dipropylene glycol monomethyl ether as a part of the organic solvent (E), and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties. It is also preferable to include at least one kind. Both the first liquid as a part of the organic solvent (E), dipropylene glycol monomethyl ether, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties In the case of containing, the first liquid may or may not contain titanium oxide.
  • the first liquid may contain dipropylene glycol monomethyl ether or diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), and has an initial boiling point of 150 in the distillation property.
  • a naphtha having an end point in distillation properties of 150 ° C. or more may be included, and an naphtha having an end point in distillation properties of 220 ° C. or less may be included.
  • the second liquid may contain diethylene glycol monoethyl ether acetate or dipropylene glycol monomethyl ether as a part of the organic solvent (E), and may have an initial boiling point in distillation properties. May contain naphtha having a temperature of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower.
  • the photosensitive composition is at least 2 selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties. Including species.
  • the photosensitive composition includes three kinds of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. May be.
  • the photosensitive composition contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or diethylene glycol monoethyl ether acetate and distilled. It is preferable to include at least naphtha having an initial boiling point of 150 ° C. or more in properties and an end point of 290 ° C. or less in distillation properties.
  • the photosensitive composition preferably contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate.
  • the photosensitive composition may contain naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
  • the photosensitive composition is composed of diethylene glycol monoethyl ether acetate and an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. It preferably contains at least some naphtha.
  • the first liquid preferably contains dipropylene glycol monomethyl ether.
  • the photosensitive composition has dipropylene glycol monomethyl ether and an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. It preferably contains at least some naphtha.
  • the first liquid may contain diethylene glycol monoethyl ether acetate.
  • naphtha having an initial boiling point of 150 ° C. or more in the distillation property and an end point of distillation property of 290 ° C. or less in the photosensitive composition is the first in the distillation property.
  • a naphtha having a boiling point of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower is preferable.
  • the first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), has an initial boiling point of 150 ° C. or more in distillation properties, and an end point in distillation properties of 290 ° C. It is preferable to include at least two selected from the group consisting of the following naphtha. In this case, the mixing property of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.
  • the first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), has an initial boiling point of 150 ° C. or more in distillation properties, and an end point in distillation properties of 290 ° C. You may include three types with the following naphtha.
  • the first liquid contains, as a part of the organic solvent (E), at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties. It is preferable that at least 150 degreeC and the naphtha whose end point in distillation property is 290 degrees C or less are included. In this case, the mixing property of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.
  • the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate. In this case, the first liquid may contain naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
  • the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties.
  • the first liquid preferably contains dipropylene glycol monomethyl ether.
  • the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
  • the first liquid may contain diethylene glycol monoethyl ether acetate.
  • the photosensitive composition may be dipropylene glycol monomethyl ether as the organic solvent. And diethylene glycol monoethyl ether acetate and at least two selected from the group consisting of naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Distillation properties in the first liquid
  • the naphtha having an initial boiling point of 150 ° C. or higher and an end point in distillation properties of 290 ° C. or lower is preferably a naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower.
  • the first liquid may not contain diethylene glycol monoethyl ether acetate.
  • the initial boiling point in distillation properties is 150 ° C. or higher, and the end point in distillation properties is 220 ° C. It may contain at least two kinds selected from the group consisting of the following naphtha.
  • the second liquid is diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether as part of the organic solvent (E), the initial boiling point in the distillation property is 150 ° C. or higher, and the end point in the distillation property is 220 ° C. You may include three types with the following naphtha.
  • the second liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether. In this case, the second liquid may contain naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 220 ° C. or lower in distillation properties.
  • the second liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 220 ° C. or lower in distillation properties.
  • the second liquid preferably contains dipropylene glycol monomethyl ether.
  • the second liquid is used as a part of the organic solvent (E). It is preferable to include at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties.
  • the second liquid may contain diethylene glycol monoethyl ether acetate.
  • the second liquid may not contain diethylene glycol monoethyl ether acetate.
  • the content of the organic solvent (E) is not particularly limited. In consideration of the coating properties of the photosensitive composition, the organic solvent (E) can be used in an appropriate content. In 100% by weight of the photosensitive composition after mixing, the total content of the organic solvent (E) (the total content of the organic solvent (E1) and the organic solvent (E2)) is preferably 10% by weight. Above, more preferably 15% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.
  • the first and second liquids of the two-liquid mixed type are used in the first and second liquids as a whole.
  • the content of the organic solvent (E1) contained in the first liquid and the content of the organic solvent (E2) contained in the second liquid are 1:99 to 99: 1 in a weight ratio. It is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and particularly preferably 3: 7 to 7: 3.
  • the organic solvent (E) contained in the first liquid in a total content of 100% by weight of the organic solvent (E) contained in the photosensitive composition (
  • the weight ratio of the content of E1) and the content of the organic solvent (E2) contained in the second liquid is preferably 1:99 to 99: 1, and 1: 9 to 9 : 1 is more preferable, 2: 8 to 8: 2 is still more preferable, and 3: 7 to 7: 3 is particularly preferable.
  • the content of diethylene glycol monoethyl ether acetate may be 30% by weight or more in 100% by weight of the whole of the first and second liquids of the two-component mixed type and 100% by weight of the photosensitive composition after mixing. In 100% by weight of the first liquid, the content of diethylene glycol monoethyl ether acetate may be 50% by weight or less, or 55% by weight or more.
  • the first liquid contains two kinds of organic solvents
  • the second liquid contains two kinds of organic solvents
  • the first liquid and the second liquid have a large content.
  • the content of the organic solvent and the content of the organic solvent having a lower content are preferably in a weight ratio of 1:99 to 99: 1, more preferably 1: 9 to 9: 1.
  • it is 2: 8 to 8: 2, more preferably 3: 7 to 7: 3.
  • the content of the first liquid and the second liquid is the highest.
  • the content of the organic solvent having the largest amount and the content of the organic solvent having the second largest content are preferably 1:99 to 99: 1 by weight, more preferably 1: 9 to 9: 1.
  • it is 2: 8 to 8: 2, more preferably 3: 7 to 7: 3.
  • the lower limit of the content of the organic solvent having the smallest content is not particularly limited.
  • the photosensitive composition preferably contains a polymerizable monomer as a component different from the polymerizable polymer (A) having a carboxyl group.
  • the photosensitive composition preferably contains both a polymerizable polymer (A) having a carboxyl group and a polymerizable monomer.
  • the polymerizable monomer is polymerizable and can be polymerized.
  • the polymerizable monomer is not particularly limited. As for the said polymerizable monomer, only 1 type may be used and 2 or more types may be used together.
  • the polymerizable monomer is preferably a polymerizable unsaturated group-containing monomer.
  • the polymerizable unsaturated group in the polymerizable monomer include functional groups having a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl ether group.
  • a (meth) acryloyl group is preferable because the crosslinking density of the resist film can be increased.
  • the polymerizable unsaturated group-containing monomer is preferably a compound having a (meth) acryloyl group.
  • the compound having the (meth) acryloyl group include a di (meth) acrylate modified product of glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, polyhydric alcohol, and ethylene oxide adduct of polyhydric alcohol.
  • a polyhydric (meth) acrylate modified product of a propylene oxide adduct of a polyhydric alcohol a (meth) acrylate modified product of phenol, an ethylene oxide adduct of phenol or a propylene oxide adduct of phenol, glycerin diglycidyl ether or (Meth) acrylate modified products of glycidyl ether such as trimethylolpropane triglycidyl ether and melamine (meth) acrylate are exemplified.
  • Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate.
  • Examples of the (meth) acrylate of phenol include phenoxy (meth) acrylate and di (meth) acrylate modified products of bisphenol A.
  • (Meth) acryloyl means acryloyl and methacryloyl.
  • (Meth) acryl means acrylic and methacrylic.
  • (Meth) acrylate means acrylate and methacrylate.
  • the content of the polymerizable monomer is 100% by weight in total of the polymerizable monomer and the polymerizable polymer (A) having a carboxyl group.
  • it is 5 weight% or more, Preferably it is 50 weight% or less.
  • a photosensitive composition can fully be hardened as content of the said polymerizable monomer is more than the said minimum and below the said upper limit. Furthermore, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is hardly yellowed.
  • the photosensitive composition preferably contains an antioxidant.
  • the antioxidant preferably has a Lewis basic site.
  • the antioxidant is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Is preferred.
  • the antioxidant is preferably a phenolic antioxidant. That is, the photosensitive composition preferably contains 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, and IRGANOX 295 (all of which are manufactured by Ciba Japan), ADK STAB 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, and ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, and Sumizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and S milizer GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANO
  • Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine.
  • Commercially available phosphoric antioxidants include ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, and ADK STAB 1178 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP (all of which are manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all of which are manufactured by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 Re also be mentioned Johoku Chemical Industry 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- And diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.
  • the content of the antioxidant is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts by weight or less with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. More preferably, it is 15 parts by weight or less.
  • the content of the antioxidant is not less than the above lower limit and not more than the upper limit, a more excellent resist film can be formed by heat yellowing.
  • the photosensitive composition 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, a surface modification agent.
  • a quality agent, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor may be included.
  • the above-mentioned photosensitive composition can be prepared, for example, by stirring and mixing the blending components 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 two-liquid mixed type first and second liquids according to the present invention are preferably used for forming a resist film of an LED device, and more preferably used for forming a solder resist film.
  • the two-liquid mixed type first and second liquids according to the present invention are preferably resist compositions, and are preferably solder resist compositions.
  • a method for manufacturing a printed wiring board according to the present invention is a method for manufacturing a printed wiring board comprising a printed wiring board main body having a circuit on its surface and a resist film laminated on the surface of the printed wiring board main body provided with the circuit. Is the method.
  • the resist film is formed of a two-liquid mixed type first and second liquid according to the present invention.
  • FIG. 1 schematically shows an example of an LED device having a solder resist film formed using a two-liquid mixed type first and second liquid according to an embodiment of the present invention in a partially cutaway front sectional view. .
  • a resist film 3 formed of a two-liquid mixed type first and second liquid is laminated on an upper surface 2a of a substrate 2.
  • the resist film 3 is a pattern film. Therefore, the resist film 3 is not formed in a part of the upper surface 2 a of the substrate 2.
  • Electrodes 4a and 4b are provided on the upper surface 2a of the substrate 2 where the resist film 3 is not formed.
  • the substrate 2 is preferably a printed wiring board body.
  • the LED chip 7 is laminated on the upper surface 3 a of the resist film 3.
  • An LED chip 7 is laminated on the substrate 2 via the resist film 3.
  • Terminals 8 a and 8 b are provided on the outer peripheral edge of the lower surface 7 a of the LED chip 7.
  • the terminals 8a and 8b are electrically connected to the electrodes 4a and 4b by the solder 9a and 9b. By this electrical connection, power can be supplied to the LED chip 7.
  • Acrylic polymer 1 (polymer having a carboxyl group, acrylic polymer 1 obtained in Synthesis Example 1 below)
  • 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 wt% (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 60 mg KOH / g, a weight average molecular weight of 15000, and a double bond equivalent of 1000.
  • this solution is referred to as acrylic polymer 1.
  • Acrylic polymer 2 (polymerizable polymer having a carboxyl group, acrylic polymer 2 obtained in Synthesis Example 2 below)
  • TMPTA (acrylic monomer, trimethylolpropane triacrylate, specific gravity 1.1)
  • TPO photopolymerization initiator that is a photo radical generator, manufactured by BASF Japan
  • Irgacure 819 photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan Ltd.
  • R-830 titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the sulfuric acid method
  • Ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel Chemical Industries, dipole moment 1 Debye or more, specific gravity 1.0)
  • Solvesso 150 Naphtha, ExxonMobil Corporation, initial boiling point 189 ° C. in distillation properties, end point 210 ° C. in distillation properties
  • Solvesso 100 (naphtha, manufactured by ExxonMobil, initial boiling point 165 ° C. in distillation properties, end point 174 ° C. in distillation properties)
  • Solvesso 200 Naphtha, ExxonMobil Corporation, initial boiling point 230 ° C. in distillation properties, end point 283 ° C. in distillation properties
  • Example 1 15 g of the acrylic polymer 1 obtained in Synthesis Example 1, 5 g of DPHA (dipentaerythritol hexaacrylate), 2 g of TPO (a photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan), and CR-50 ( 40 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) and 25 g of Solvesso 150 (naphtha, manufactured by ExxonMobil Corp.) are mixed and mixed for 3 minutes with a blender (Nentaro SP-500, manufactured by Shinky Corp.) The mixture was obtained by a roll to obtain a mixture. Thereafter, the obtained mixture was degassed for 3 minutes using SP-500 to obtain a first liquid.
  • DPHA dipentaerythritol hexaacrylate
  • TPO a photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan
  • CR-50 40 g of titanium oxide
  • Examples 2 to 49 Reference Examples 1 to 11 and Comparative Examples 1 to 19
  • the first and second liquids were the same as in Example 1 except that the types and amounts of the materials used in the first liquid and the second liquid were changed as shown in Tables 1 to 8 below.
  • a two-liquid mixed type first and second liquid photosensitive composition before mixing
  • the first liquid and the second liquid are placed in a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.), and the resist material is stirred for 1 minute at 50 rpm by an automatic ink kneader manufactured by Mesh Co., Ltd.
  • a photosensitive composition after mixing was prepared. Further, the first liquid and the second liquid are put into a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.), and the resist is stirred for 5 minutes at 50 rpm by an automatic ink kneader manufactured by Mesh Co.
  • a material (photosensitive composition after mixing) was prepared.
  • a 100 ⁇ 100 mm FR-4 substrate with a copper foil attached to the surface was prepared.
  • the resist material immediately after stirring was applied to the surface of the FR-4 substrate on which the copper foil was attached by screen printing to form a resist material layer. The appearance of the resist material layer on the substrate was visually observed.
  • the mixing property of the first and second liquids was determined according to the following criteria.
  • Example 5 and Example 29 are more preferable than Example 33.
  • the photosensitive composition was uniformly mixed.
  • the evaluation results of the mixing properties of the two liquids of Example 30, Example 31 and Example 34 are all “A”, but Example 30 and Example 31 are much shorter than Example 34.
  • the photosensitive composition was uniformly mixed.
  • the evaluation results of the mixing properties of the two liquids of Example 35, Example 37, and Example 39 are all “A”, but Example 35 and Example 37 are much shorter than Example 39. Over time, the photosensitive composition was uniformly mixed.

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Abstract

Provided are a first and second liquid that are two-liquid mixing type and that have superior miscibility of the first and second liquid. The two-liquid mixing first and second liquids are liquids for obtaining a photosensitive composition that is a mixture. The photosensitive composition contains at least two selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a naphtha having, in the distillation characteristics thereof, a first drop point of at least 150°C and a last point of no greater than 290°C. The first liquid contains a polymeric polymer. The second liquid contains a compound having a cyclic ether group. The first and second liquids contain at least one selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a naphtha having, in the distillation characteristics thereof, a first drop point of at least 150°C and a last point of no greater than 290°C.

Description

２液混合型の第１，第２の液及びプリント配線板の製造方法Two-liquid mixed type first and second liquid and method for producing printed wiring board
　本発明は、混合物である感光性組成物を得るための２液混合型の第１，第２の液に関する。本発明は、より詳細には、基板上にソルダーレジスト膜を形成したり、発光ダイオードチップが搭載される基板上に光を反射するレジスト膜を形成したりするために好適に用いられる２液混合型の第１，第２の液、並びに該２液混合型の第１，第２の液を用いたプリント配線板の製造方法に関する。 The present invention relates to a two-component mixed type first and second solution for obtaining a photosensitive composition as a mixture. In more detail, the present invention is a two-liquid mixture suitably used for forming a solder resist film on a substrate or forming a resist film that reflects light on a substrate on which a light emitting diode chip is mounted. The present invention relates to a method for manufacturing a printed wiring board using first and second liquids of a mold and the first and second liquids of the two liquid mixture type.
　プリント配線板を高温のはんだから保護するための保護膜として、ソルダーレジスト膜が広く用いられている。 Solder resist films are widely used as protective films for protecting printed wiring boards from high-temperature solder.
　また、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材料が開示されている。 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. A resist material further containing an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and a cured adhesion-imparting agent is disclosed.
　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材料が開示されている。 Patent Document 2 below discloses a white solder resist material containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, a rutile titanium oxide, and a diluent. Yes.
特開２００７－２４９１４８号公報JP 2007-249148 A 特開２００７－３２２５４６号公報JP 2007-322546 A
　基板上にレジスト膜を形成するために、特許文献１～２に記載のような従来のレジスト材料を基板上に塗工した場合には、レジスト材料を均一に塗工できず、塗工むらが生じることがある。例えば、スクリーン印刷により、従来のレジスト材料を基板上に塗工した場合には、塗工されたレジスト材料層において、スジ状のむらが見られることがある。
　本発明の目的は、２液混合型の第１，第２の液であって、該第１，第２の液の混合性に優れており、第１，第２の液が混合された混合物である感光性組成物を塗工対象部材上に塗工したときに、むらを抑制して均一に塗工することができる２液混合型の第１，第２の液、並びに該２液混合型の第１，第２の液を用いたプリント配線板の製造方法を提供することである。 When a conventional resist material as described in Patent Documents 1 and 2 is applied on a substrate in order to form a resist film on the substrate, the resist material cannot be applied uniformly, resulting in uneven coating. May occur. For example, when a conventional resist material is applied onto a substrate by screen printing, streaky irregularities may be seen in the applied resist material layer.
An object of the present invention is a two-liquid mixed type first and second liquid, which is excellent in the mixing property of the first and second liquids, and is a mixture in which the first and second liquids are mixed. When the photosensitive composition is applied onto a coating target member, the two-liquid mixed type first and second liquids that can be uniformly coated while suppressing unevenness, and the two-liquid mixing It is to provide a method for manufacturing a printed wiring board using first and second liquids of a mold.
　本発明の広い局面によれば、混合物である感光性組成物を得るための２液混合型の第１，第２の液であり、該２液混合型の第１，第２の液は該第１，第２の液が混合される前の液であり、上記第１，第２の液が混合された混合物である感光性組成物が全体で、カルボキシル基を有する重合性重合体と、光重合開始剤と、環状エーテル基を有する化合物と、酸化チタンと、有機溶剤とを含み、上記感光性組成物が、上記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含み、上記第１の液が、上記重合性重合体を含み、かつ上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第２の液が、上記環状エーテル基を有する化合物を含み、かつ上記有機溶剤の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第１の液が、上記光重合開始剤を含むか、上記酸化チタンを含むか、又は上記光重合開始剤と上記酸化チタンとの双方を含み、上記第１の液が上記光重合開始剤を含まない場合には上記第２の液が上記光重合開始剤を含み、上記第１の液が上記酸化チタンを含まない場合には上記第２の液が上記酸化チタンを含む、２液混合型の第１，第２の液が提供される。 According to a wide aspect of the present invention, there are two-liquid mixed type first and second liquids for obtaining a photosensitive composition which is a mixture, and the two-liquid mixed type first and second liquids are The photosensitive composition which is a liquid before the first and second liquids are mixed, and is a mixture in which the first and second liquids are mixed, and a polymerizable polymer having a carboxyl group as a whole, A photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent, wherein the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and distillation properties as the organic solvent. Including at least two selected from the group consisting of naphtha having an initial boiling point of 150 ° C. or higher and an end point in distillation properties of 290 ° C. or lower, wherein the first liquid contains the polymerizable polymer, and Yes As a part of the solvent, at least one selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial distillation point of 150 ° C. or more in distillation properties and an end point of distillation properties of 290 ° C. or less. And the second liquid contains a compound having the cyclic ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the initial boiling point in the distillation property is 150. At least one selected from the group consisting of naphtha having an endpoint in distillation properties of 220 ° C. or lower, and the first liquid contains the photopolymerization initiator or the titanium oxide, Or both the photopolymerization initiator and the titanium oxide And when the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, A two-liquid mixed type first and second liquid containing two titanium oxides are provided.
　本発明に係るプリント配線板の製造方法は、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回路が設けられた表面に積層されたソルダーレジスト膜とを備えるプリント配線板の製造方法であり、第１，第２の液を混合し、上記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物を得る工程と、回路を表面に有するプリント配線板本体の回路が設けられた表面上に、上記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物を塗工して、上記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ソルダーレジスト膜を形成する工程とを備え、上記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物が全体で、カルボキシル基を有する重合性重合体と、光重合開始剤と、環状エーテル基を有する化合物と、酸化チタンと、有機溶剤とを含み、上記感光性組成物が、上記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含み、上記第１の液が、上記重合性重合体を含み、かつ上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第２の液が、上記環状エーテル基を有する化合物を含み、かつ上記有機溶剤の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第１の液が、上記光重合開始剤を含むか、上記酸化チタンを含むか、又は上記光重合開始剤と上記酸化チタンとの双方を含み、上記第１の液が上記光重合開始剤を含まない場合には上記第２の液が上記光重合開始剤を含み、上記第１の液が上記酸化チタンを含まない場合には上記第２の液が上記酸化チタンを含む。 A method of manufacturing a printed wiring board according to the present invention is a manufacturing of a printed wiring board including a printed wiring board main body having a circuit on the surface and a solder resist film laminated on the surface of the printed wiring board main body provided with the circuit. A method of mixing a first and second liquid to obtain a photosensitive composition which is a solder resist composition in which the first and second liquids are mixed, and a printed wiring board having a circuit on the surface A photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed, is applied onto the surface of the main body provided with the circuit, and the circuit of the printed wiring board main body is provided. Forming a solder resist film laminated on the surface, and the photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed, has a polymerizable weight having a carboxyl group as a whole. Coalescence , A photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent, wherein the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and distillation as the organic solvent. Including at least two selected from the group consisting of naphtha having an initial boiling point of 150 ° C. or higher in properties and an end point in distillation properties of 290 ° C. or lower, and the first liquid includes the polymerizable polymer, and As part of the organic solvent, at least selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less. 1 type is included, and the second liquid is the ring Including a compound having an ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point in distillation properties of 150 ° C. or higher, and an end point in distillation properties of 220 ° C. or lower. It contains at least one selected from the group consisting of a certain naphtha, and the first liquid contains the photopolymerization initiator, the titanium oxide, or the photopolymerization initiator and the titanium oxide. In the case where the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and the first liquid does not contain the titanium oxide. The second liquid contains the titanium oxide.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法のある特定の局面では、上記第１の液が、上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含む。 In a specific aspect of the first and second liquid-mixed first and second liquids according to the present invention and the method for producing a printed wiring board according to the present invention, the first liquid may be used as a part of the organic solvent. It includes at least two selected from the group consisting of propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法の他の特定の局面では、上記第１の液が、上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む。 In another specific aspect of the two-liquid mixed type first and second liquids according to the present invention and the method for producing a printed wiring board according to the present invention, the first liquid is a part of the organic solvent, Dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate at least, or diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties Including at least.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法の他の特定の局面では、上記第１の液が、上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む。
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法の別の特定の局面では、上記感光性組成物が、上記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、上記第１の液における上記蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサが、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサである。 In another specific aspect of the two-liquid mixed type first and second liquids according to the present invention and the method for producing a printed wiring board according to the present invention, the first liquid is a part of the organic solvent, It contains at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
In another specific aspect of the first and second liquid-mixed first and second liquids according to the present invention and the method for producing a printed wiring board according to the present invention, the photosensitive composition contains dipropylene glycol as the organic solvent. Including at least two selected from the group consisting of monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower, in the first liquid A naphtha having an initial distillation point in the distillation property of 150 ° C. or more and an end point in the distillation property of 290 ° C. or less is a naphtha having an initial distillation point in the distillation property of 150 ° C. or more and an end point in the distillation property of 220 ° C. or less.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法の他の特定の局面では、上記第１の液が上記光重合開始剤を含む。 In another specific aspect of the two-liquid mixed type first and second liquids according to the present invention and the printed wiring board manufacturing method according to the present invention, the first liquid contains the photopolymerization initiator.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法の他の特定の局面では、上記第１の液が上記酸化チタンを含む。 In another specific aspect of the two-liquid mixed type first and second liquids according to the present invention and the method for producing a printed wiring board according to the present invention, the first liquid contains the titanium oxide.
　本発明に係る２液混合型の第１，第２の液及び本発明に係るプリント配線板の製造方法のさらに他の特定の局面では、上記第１の液が上記光重合開始剤と上記酸化チタンとの双方を含む。 In still another specific aspect of the first and second liquid-mixed first and second liquids according to the present invention and the printed wiring board manufacturing method according to the present invention, the first liquid includes the photopolymerization initiator and the oxidation. Including both titanium.
　本発明に係る２液混合型の第１，第２の液では、上記第１，第２の液が混合された感光性組成物がソルダーレジスト組成物として好適に用いられる。本発明に係る２液混合型の第１，第２の液では、上記第１，第２の液が混合された感光性組成物がソルダーレジスト組成物であることが好ましい。 In the two-liquid mixed type first and second liquids according to the present invention, the photosensitive composition in which the first and second liquids are mixed is suitably used as the solder resist composition. In the two-liquid mixed type first and second liquids according to the present invention, the photosensitive composition in which the first and second liquids are mixed is preferably a solder resist composition.
　本発明に係る２液混合型の第１，第２の液は、混合物である感光性組成物を得るための２液混合型の第１，第２の液であり、該２液混合型の第１，第２の液は該第１，第２の液が混合される前の液であり、上記第１，第２の液が混合された混合物である感光性組成物が全体で、カルボキシル基を有する重合性重合体と光重合開始剤と環状エーテル基を有する化合物と酸化チタンと有機溶剤とを含み、上記感光性組成物が、上記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含み、上記第１の液が、上記重合性重合体を含みかつ上記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第２の液が、上記環状エーテル基を有する化合物を含みかつ上記有機溶剤の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含み、上記第１の液が、上記光重合開始剤を含むか、上記酸化チタンを含むか、又は上記光重合開始剤と上記酸化チタンとの双方を含むので、上記第１，第２の液の混合性に優れており、混合後の感光性組成物を塗工対象部材上に塗工したときに、むらを抑制して均一に塗工することができる。 The two-liquid mixed type first and second liquids according to the present invention are two-liquid mixed type first and second liquids for obtaining a photosensitive composition as a mixture. The first and second liquids are liquids before the first and second liquids are mixed, and the photosensitive composition, which is a mixture of the first and second liquids, is a carboxyl group as a whole. A polymerizable polymer having a group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, and an organic solvent, wherein the photosensitive composition includes dipropylene glycol monomethyl ether, diethylene glycol monoethyl as the organic solvent. It contains at least two selected from the group consisting of ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less, and the first liquid is the polymerizable polymer Including and As part of the organic solvent, at least selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 290 ° C. or less. 1 type, the second liquid contains the compound having the cyclic ether group and, as a part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and the initial boiling point in distillation properties are Whether the first liquid contains the photopolymerization initiator or the titanium oxide, including at least one selected from the group consisting of naphtha having a distillation property of 150 ° C. or higher and an end point in distillation property of 220 ° C. or lower. Or the photopolymerization initiator and the titanium oxide Therefore, when the photosensitive composition after mixing is coated on the coating target member, the coating is uniformly performed while suppressing unevenness. can do.
図１は、本発明の一実施形態に係る２液混合型の第１，第２の液を用いたレジスト膜を有する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 having a resist film using a two-liquid mixed type first and second liquid according to an embodiment of the present invention.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明に係る２液混合型の第１，第２の液は、混合物である感光性組成物を得るために用いられる。本発明に係る２液混合型の第１，第２の液は、混合物である感光性組成物を得るために用いられるキットである。本発明に係る２液混合型の第１，第２の液は混合されて用いられる。本発明に係る２液混合型の第１，第２の液は該第１，第２の液が混合される前の液である。混合される前の第１，第２の液は、混合前の感光性組成物である。本発明に係る２液混合型の第１，第２の液が混合された混合物である感光性組成物は全体で、カルボキシル基を有する重合性重合体（Ａ）と、光重合開始剤（Ｂ）と、環状エーテル基を有する化合物（Ｃ）と、酸化チタン（Ｄ）と、有機溶剤（Ｅ）（以下、感光性組成物全体に含まれている有機溶剤を、有機溶剤（Ｅ）と記載することがある）とを含む。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、混合された該感光性組成物は全体で、カルボキシル基を有する重合性重合体（Ａ）と、光重合開始剤（Ｂ）と、環状エーテル基を有する化合物（Ｃ）と、酸化チタン（Ｄ）と、有機溶剤（Ｅ）とを含む。 The two-liquid mixed type first and second liquids according to the present invention are used to obtain a photosensitive composition which is a mixture. The two-liquid mixed type first and second liquids according to the present invention are kits used for obtaining a photosensitive composition as a mixture. The two-liquid mixed type first and second liquids according to the present invention are mixed and used. The two-liquid mixed type first and second liquids according to the present invention are liquids before the first and second liquids are mixed. The first and second liquids before being mixed are the photosensitive compositions before being mixed. The photosensitive composition which is a mixture in which the first and second liquids of the two liquid mixture type according to the present invention are mixed as a whole is a polymerizable polymer (A) having a carboxyl group and a photopolymerization initiator (B ), A compound (C) having a cyclic ether group, titanium oxide (D), and an organic solvent (E) (hereinafter, the organic solvent contained in the entire photosensitive composition is referred to as an organic solvent (E). May be included). The mixture in which the first and second liquids are mixed is a photosensitive composition, and the mixed photosensitive composition as a whole is a polymerizable polymer (A) having a carboxyl group and a photopolymerization initiator. (B), the compound (C) which has a cyclic ether group, a titanium oxide (D), and the organic solvent (E) are included.
　上記感光性組成物は、上記有機溶剤（Ｅ）として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含む。 The photosensitive composition includes, as the organic solvent (E), dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and 290 ° C. or lower in distillation properties. At least two selected from the group consisting of:
　上記第１の液は、上記重合性重合体（Ａ）を含み、かつ上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含む。上記第２の液は、上記環状エーテル基を有する化合物（Ｃ）を含み、かつ上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含む。 The first liquid contains the polymerizable polymer (A) and, as a part of the organic solvent (E), dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and an initial boiling point of 150 in distillation properties are 150. It contains at least one selected from the group consisting of naphtha having an end point in the distillation property of 290 ° C. or lower. The second liquid contains the compound (C) having the cyclic ether group, and as part of the organic solvent (E), diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial distillation in distillation properties. It includes at least one selected from the group consisting of naphtha having a point of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower.
　上記第１の液は、上記光重合開始剤（Ｂ）を含むか、上記酸化チタン（Ｄ）を含むか、又は上記光重合開始剤（Ｂ）と上記酸化チタン（Ｄ）との双方を含む。上記第１の液が上記光重合開始剤（Ｂ）を含まない場合には、上記第２の液が上記光重合開始剤（Ｂ）を含む。上記第１の液が上記酸化チタン（Ｄ）を含まない場合には、上記第２の液が上記酸化チタン（Ｄ）を含む。上記光重合開始剤（Ｂ）及び上記酸化チタン（Ｄ）はそれぞれ、第１の液に含まれていてもよく、第２の液に含まれていてもよく、第１の液と第２の液との双方に含まれていてもよい。 The first liquid contains the photopolymerization initiator (B), contains the titanium oxide (D), or contains both the photopolymerization initiator (B) and the titanium oxide (D). . When the first liquid does not contain the photopolymerization initiator (B), the second liquid contains the photopolymerization initiator (B). When the first liquid does not contain the titanium oxide (D), the second liquid contains the titanium oxide (D). The photopolymerization initiator (B) and the titanium oxide (D) may each be contained in the first liquid, may be contained in the second liquid, the first liquid, and the second liquid It may be contained in both of the liquid.
　また、本発明に係る２液混合型の第１，第２の液が後述する重合性単量体を含んでいたり、後述する酸化防止剤を含んでいたりする場合には、重合性単量体及び酸化防止剤はそれぞれ、第１の液に含まれていてもよく、第２の液に含まれていてもよく、第１の液と第２の液との双方に含まれていてもよい。 In addition, when the two-liquid mixed type first and second liquids according to the present invention contain a polymerizable monomer described later or an antioxidant described later, the polymerizable monomer And the antioxidant may be contained in the first liquid, may be contained in the second liquid, or may be contained in both the first liquid and the second liquid. .
　本発明に係る２液混合型の第１，第２の液における上記構成の採用により、上記第１，第２の液の混合性を高めることができる。さらに、基板などの塗工対象部材上に、混合後の感光性組成物を塗工したときに、酸化チタンが大きく起因して生じるむらを抑制して均一に塗工することができる。特に、混合後の感光性組成物をスクリーン印刷により塗工したときに、スジ状のむらを抑制できる。本発明に係る２液混合型の第１，第２の液は、スクリーン印刷により塗工される２液混合型の第１，第２の液であることが好ましい。 By adopting the above-described configuration in the two-liquid mixed type first and second liquids according to the present invention, the mixing properties of the first and second liquids can be enhanced. Furthermore, when the photosensitive composition after mixing is applied onto a coating target member such as a substrate, it can be uniformly applied while suppressing unevenness caused largely by titanium oxide. In particular, when the photosensitive composition after mixing is applied by screen printing, streaky unevenness can be suppressed. The two-liquid mixed type first and second liquids according to the present invention are preferably two-liquid mixed type first and second liquids to be applied by screen printing.
　上記光重合開始剤（Ｂ）は、第２の液ではなく、第１の液に含まれていることが好ましい。この場合には、上記第１，第２の液の混合性がより一層高くなり、かつ感光性組成物をより一層均一に塗工できる。 It is preferable that the photopolymerization initiator (B) is contained in the first liquid, not the second liquid. In this case, the mixing properties of the first and second liquids are further enhanced, and the photosensitive composition can be applied more uniformly.
　上記酸化チタン（Ｄ）は、第２の液ではなく、第１の液に含まれていることが好ましい。この場合には、酸化チタン（Ｄ）の分散性が高くなり、更に上記第１，第２の液の混合性がより一層高くなり、かつ感光性組成物をより一層均一に塗工できる。 The titanium oxide (D) is preferably contained in the first liquid, not the second liquid. In this case, the dispersibility of titanium oxide (D) is increased, the mixing properties of the first and second liquids are further increased, and the photosensitive composition can be applied more uniformly.
　上記光重合開始剤（Ｂ）と上記酸化チタン（Ｄ）との双方が、第２の液ではなく、第１の液に含まれていることが好ましい。この場合には、酸化チタン（Ｄ）の分散性がより一層高くなり、更に上記第１，第２の液の混合性が更に一層高くなり、かつ感光性組成物を更に一層均一に塗工できる。 It is preferable that both the photopolymerization initiator (B) and the titanium oxide (D) are contained in the first liquid instead of the second liquid. In this case, the dispersibility of titanium oxide (D) is further enhanced, the mixing properties of the first and second liquids are further enhanced, and the photosensitive composition can be applied more uniformly. .
　以下、本発明に係る２液混合型の第１，第２の液、並びに混合後の感光性組成物に含まれている各成分の詳細を説明する。 Hereinafter, the details of the respective components contained in the first and second liquids of the two-component mixed type according to the present invention and the photosensitive composition after mixing will be described.
　（重合性重合体（Ａ））
　上記重合性重合体（Ａ）はカルボキシル基を有する。カルボキシル基を有する重合性重合体（Ａ）は重合性を有し、重合可能である。上記重合性重合体（Ａ）がカルボキシル基を有することで、感光性組成物の現像性が良好になる。上記重合性重合体（Ａ）としては、例えば、カルボキシル基を有するアクリル樹脂、カルボキシル基を有するエポキシ樹脂及びカルボキシル基を有するオレフィン樹脂が挙げられる。なお、「樹脂」は、固形樹脂に限定されず、液状樹脂及びオリゴマーも含む。 (Polymerizable polymer (A))
The polymerizable polymer (A) has a carboxyl group. The polymerizable polymer (A) having a carboxyl group has polymerizability and can be polymerized. When the polymerizable polymer (A) has a carboxyl group, the developability of the photosensitive composition is improved. Examples of the polymerizable polymer (A) include an acrylic resin having a carboxyl group, an epoxy resin having a carboxyl group, and an olefin resin having a carboxyl group. The “resin” is not limited to a solid resin, and includes a liquid resin and an oligomer.
　上記重合性重合体（Ａ）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。 The polymerizable polymer (A) is preferably the following carboxyl group-containing resins (a) to (e).
　（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 (A) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having a polymerizable unsaturated double bond
　（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 (B) Carboxyl group-containing resin obtained by reaction of carboxyl group-containing (meth) acrylic copolymer resin (b1) and compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond in one molecule
　（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 (C) Reaction of an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and a polymerizable unsaturated double bond in each molecule and a compound having a polymerizable unsaturated double bond A carboxyl group-containing resin obtained by reacting the secondary hydroxyl group of the resulting reaction product with a saturated or unsaturated polybasic acid anhydride
　（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、生成したカルボキシル基を有するポリマーに、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 (D) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting polymer having a carboxyl group has one epoxy group and one polymerizable unsaturated double bond in each molecule. Hydroxyl and carboxyl group-containing resin obtained by reacting a compound having
　（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又は不飽和多塩基酸無水物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又は不飽和多塩基酸無水物をさらに反応させて得られる樹脂
　上記感光性組成物１００重量％中、上記カルボキシル基を有する重合性重合体（Ａ）の含有量は、好ましくは３重量％以上、より好ましくは５重量％以上、好ましくは５０重量％以下、より好ましくは４０重量％以下である。上記カルボキシル基を有する重合性重合体（Ａ）の含有量が上記下限以上及び上記上限以下であると、感光性組成物の硬化性が良好になる。 (E) A resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or an epoxy compound having an aromatic ring and at least one unsaturated double bond Resin obtained by further reacting with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride after reacting with a carboxyl group-containing compound Polymerization having the carboxyl group in 100% by weight of the photosensitive composition The content of the polymer (A) is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the polymerizable polymer (A) having a carboxyl group is not less than the above lower limit and not more than the above upper limit, the curability of the photosensitive composition is improved.
　（光重合開始剤（Ｂ））
　上記感光性組成物は、光重合開始剤（Ｂ）を含むので、光の照射により感光性組成物を硬化させることができる。光重合開始剤（Ｂ）は特に限定されない。光重合開始剤（Ｂ）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。 (Photopolymerization initiator (B))
Since the said photosensitive composition contains a photoinitiator (B), a photosensitive composition can be hardened by irradiation of light. The photopolymerization initiator (B) is not particularly limited. As for a photoinitiator (B), only 1 type may be used and 2 or more types may be used together.
　上記光重合開始剤（Ｂ）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、及びこれらの誘導体が挙げられる。上記光重合開始剤（Ｂ）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 photopolymerization initiator (B) include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, benzoic acid ester , Acridine, phenazine, titanocene, α-aminoalkylphenone, oxime, and derivatives thereof. As for the said photoinitiator (B), only 1 type may be used and 2 or more types may be used together.
　上記カルボキシル基を有する重合性重合体（Ａ）１００重量部に対して、上記光重合開始剤（Ｂ）の含有量は好ましくは０．１重量部以上、より好ましくは１重量部以上、好ましくは３０重量部以下、より好ましくは１５重量部以下である。上記光重合開始剤（Ｂ）の含有量が上記下限以上及び上記上限以下であると、感光性組成物の感光性をより一層高めることができる。 The content of the photopolymerization initiator (B) is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. 30 parts by weight or less, more preferably 15 parts by weight or less. When the content of the photopolymerization initiator (B) is not less than the above lower limit and not more than the above upper limit, the photosensitivity of the photosensitive composition can be further enhanced.
　（環状エーテル基を有する化合物（Ｃ））
　レジスト膜の切り出し加工性を高めることなどを目的として、上記感光性組成物は、環状エーテル骨格を有する化合物（Ｃ）を含む。また、上記環状エーテル骨格を有する化合物（Ｃ）の使用により、感光性組成物の硬化性も良好になる。 (Compound having a cyclic ether group (C))
For the purpose of improving the cutout processability of the resist film, the photosensitive composition contains a compound (C) having a cyclic ether skeleton. Further, the use of the compound (C) having the cyclic ether skeleton also improves the curability of the photosensitive composition.
　上記環状エーテル骨格を有する化合物（Ｃ）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及びε－カプロラクトン変性エポキシ樹脂が挙げられる。上記環状エーテル骨格を有する化合物（Ｃ）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 compound (C) 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, tetra Glycidyl xylenoyl ethane 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 novolak type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene resin Norick type epoxy resins, silicone-modified epoxy resin and ε- caprolactone-modified epoxy resin. Only 1 type may be used for the compound (C) which has the said cyclic ether skeleton, and 2 or more types may be used together.
　上記環状エーテル骨格を有する化合物（Ｃ）は、上記カルボキシル基を有する重合性重合体（Ａ）が有する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。 The compound (C) having the cyclic ether skeleton reacts with the carboxyl group of the polymerizable polymer (A) having the carboxyl group to act to cure the photosensitive composition.
　上記カルボキシル基を有する重合性重合体（Ａ）１００重量部に対して、上記環状エーテル骨格を有する化合物（Ｃ）の含有量は好ましくは０．１重量部以上、より好ましくは１重量部以上、好ましくは５０重量部以下、より好ましくは３０重量部以下である。上記環状エーテル骨格を有する化合物（Ｃ）の含有量が上記下限以上及び上記上限以下であると、レジスト膜の電気絶縁性をより一層高めることができる。 The content of the compound (C) having a cyclic ether skeleton is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less. When the content of the compound (C) having the cyclic ether skeleton is not less than the above lower limit and not more than the above upper limit, the electrical insulation of the resist film can be further enhanced.
　（酸化チタン（Ｄ））
　上記感光性組成物は、酸化チタン（Ｄ）を含むので、反射率が高いレジスト膜などの硬化物膜を形成できる。上記感光性組成物に含まれている酸化チタン（Ｄ）は特に限定されない。酸化チタン（Ｄ）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。 (Titanium oxide (D))
Since the said photosensitive composition contains titanium oxide (D), hardened | cured material films, such as a resist film with a high reflectance, can be formed. The titanium oxide (D) contained in the said photosensitive composition is not specifically limited. As for titanium oxide (D), only 1 type may be used and 2 or more types may be used together.
　上記酸化チタン（Ｄ）を用いることによって、酸化チタン（Ｄ）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。 By using the above titanium oxide (D), it is possible to form a resist film having a high reflectance as compared with the case where an inorganic filler other than titanium oxide (D) is used.
　上記酸化チタン（Ｄ）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。 The titanium oxide (D) 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（Ｄ）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。上記酸化チタン（Ｄ）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好ましくは１０重量％以上、より好ましくは３０重量％以上、１００重量％以下である。上記酸化チタン（Ｄ）の全量が、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ってもよい。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使用により、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 (D) preferably contains rutile titanium oxide that has been surface-treated with silicon oxide or a silicone compound. In 100% by weight of the titanium oxide (D), the content of the rutile titanium oxide surface-treated with the silicon oxide or the silicone compound is preferably 10% by weight or more, more preferably 30% by weight or more and 100% by weight or less. It is. The total amount of the titanium oxide (D) may be rutile titanium oxide surface-treated with the silicon oxide or the silicone compound. By using rutile type titanium oxide surface-treated with the silicon oxide or silicone compound, 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 rutile 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 a rutile chlorine method titanium oxide, and manufactured by Ishihara Sangyo Co., Ltd., which is a rutile sulfuric acid method titanium oxide. Product number: R-550 and the like.
　上記感光性組成物１００重量％中、酸化チタン（Ｄ）の含有量は、好ましくは３重量％以上、より好ましくは１０重量％以上、更に好ましくは１５重量％以上、好ましくは８０重量％以下、より好ましくは７５重量％以下、更に好ましくは７０重量％以下である。酸化チタン（Ｄ）の含有量が上記下限以上及び上記上限以下であると、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, the content of titanium oxide (D) is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, preferably 80% by weight or less. More preferably, it is 75 weight% or less, More preferably, it is 70 weight% or less. When the content of titanium oxide (D) is not less than the above lower limit and not more than the above upper limit, the resist film is hardly yellowed when exposed to high temperatures. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.
　（有機溶剤（Ｅ））
　上記感光性組成物は、有機溶剤（Ｅ）を含む。上記第１，第２の液を混合した感光性組成物は、有機溶剤（Ｅ）を含む。上記感光性組成物は、少なくとも２種の有機溶剤を含む。上記第１の液に含まれている有機溶剤（Ｅ１）（以下、第１の液に含まれている有機溶剤を、有機溶剤（Ｅ１）と記載することがある）と、上記第２の液に含まれている有機溶剤（Ｅ２）（以下、第２の液に含まれている有機溶剤を、有機溶剤（Ｅ２）と記載することがある）とは異なることが好ましい。 (Organic solvent (E))
The photosensitive composition contains an organic solvent (E). The photosensitive composition in which the first and second liquids are mixed contains an organic solvent (E). The photosensitive composition contains at least two organic solvents. The organic solvent (E1) contained in the first liquid (hereinafter, the organic solvent contained in the first liquid may be referred to as an organic solvent (E1)), and the second liquid Is different from the organic solvent (E2) contained in the organic solvent (hereinafter, the organic solvent contained in the second liquid may be referred to as the organic solvent (E2)).
　一般的に知られている有機溶剤としては、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、ジエチレングリコールモノエ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、ナフサ等の石油系溶剤等が挙げられる。 Commonly known organic solvents include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butyl Carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, glycol ethers such as 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, diethylene glycol monoethyl ester Ether acetate, dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, and petroleum ether, petroleum solvents such as naphtha.
　上述した有機溶剤の中から、上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を必須で含む。ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサの内の少なくとも１種は、有機溶剤（Ｅ１）である。 Among the organic solvents described above, the first liquid is distilled as a part of the organic solvent (E) with dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and an initial boiling point of 150 ° C. or more in distillation properties. At least one selected from the group consisting of naphtha whose end point in properties is 290 ° C. or lower is essential. At least one of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties is an organic solvent (E1).
　また、上述した有機溶剤の中から、上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含む。ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種は、有機溶剤（Ｅ２）である。 Of the organic solvents described above, the second liquid has diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point of 150 ° C. as a part of the organic solvent (E). As mentioned above, at least 1 sort (s) selected from the group which consists of naphtha whose end point in distillation property is 220 degrees C or less is included. At least one selected from the group consisting of diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and naphtha having an initial distillation point of 150 ° C. or more in distillation properties and an end point of distillation properties of 220 ° C. or less is an organic solvent ( E2).
　このような有機溶剤（Ｅ１），（Ｅ２）を第１，第２の液にそれぞれ含有させることによって、上記第１，第２の液の混合性が顕著に良好になる。特定の上記有機溶剤（Ｅ１），（Ｅ２）の使用は、更に特定の上記有機溶剤（Ｅ１），（Ｅ２）を第１の液と第２の液とにそれぞれ分けて含有させることは、上記第１，第２の液の混合性の向上、混合された感光性組成物の塗工後のむらの抑制に大きく寄与する。 </ RTI> By including such organic solvents (E1) and (E2) in the first and second liquids, the mixing properties of the first and second liquids are remarkably improved. The use of the specific organic solvent (E1) or (E2) further includes the specific organic solvent (E1) or (E2) separately in the first liquid and the second liquid. This greatly contributes to the improvement of the mixing properties of the first and second liquids and the suppression of unevenness after the application of the mixed photosensitive composition.
　上記「蒸留性状における初留点」及び上記「蒸留性状における終点」は、ＪＩＳ　Ｋ２２５４「石油製品－蒸留試験方法」により測定される値を意味する。
上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテル、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサの内の少なくとも１種を含むことも好ましい。上記第１の液が、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテル、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとの双方を含む場合に、上記第１の液は酸化チタンを含んでいてもよく、含んでいなくてもよい。 The “initial boiling point in distillation properties” and the “end point in distillation properties” mean values measured by JIS K2254 “Petroleum products—distillation test method”.
The first liquid is dipropylene glycol monomethyl ether as a part of the organic solvent (E), and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties. It is also preferable to include at least one kind. Both the first liquid as a part of the organic solvent (E), dipropylene glycol monomethyl ether, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties In the case of containing, the first liquid may or may not contain titanium oxide.
　上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルを含んでいてもよく、ジエチレングリコールモノエチルエーテルアセテートを含んでいてもよく、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサを含んでいてもよく、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサを含んでいてもよい。 The first liquid may contain dipropylene glycol monomethyl ether or diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), and has an initial boiling point of 150 in the distillation property. A naphtha having an end point in distillation properties of 150 ° C. or more may be included, and an naphtha having an end point in distillation properties of 220 ° C. or less may be included.
　また、上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエチルエーテルアセテートを含んでいてもよく、ジプロピレングリコールモノメチルエーテルを含んでいてもよく、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサを含んでいてもよい。 The second liquid may contain diethylene glycol monoethyl ether acetate or dipropylene glycol monomethyl ether as a part of the organic solvent (E), and may have an initial boiling point in distillation properties. May contain naphtha having a temperature of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower.
　上記感光性組成物は、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含む。 The photosensitive composition is at least 2 selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties. Including species.
　上記感光性組成物は、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとの３種を含んでいてもよい。 The photosensitive composition includes three kinds of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. May be.
　感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物は、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。 From the viewpoint of more uniformly coating the photosensitive composition, the photosensitive composition contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or diethylene glycol monoethyl ether acetate and distilled. It is preferable to include at least naphtha having an initial boiling point of 150 ° C. or more in properties and an end point of 290 ° C. or less in distillation properties.
　感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物は、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むことが好ましい。この場合に、上記感光性組成物は、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサを含んでいてもよい。 From the viewpoint of more uniformly coating the photosensitive composition, the photosensitive composition preferably contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate. In this case, the photosensitive composition may contain naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
　感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物は、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第１の液は、ジプロピレングリコールモノメチルエーテルを含むことが好ましい。 From the viewpoint of more uniformly coating the photosensitive composition, the photosensitive composition is composed of diethylene glycol monoethyl ether acetate and an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. It preferably contains at least some naphtha. In this case, the first liquid preferably contains dipropylene glycol monomethyl ether.
　感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物は、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第１の液は、ジエチレングリコールモノエチルエーテルアセテートを含んでいてもよい。 From the viewpoint of more uniformly coating the photosensitive composition, the photosensitive composition has dipropylene glycol monomethyl ether and an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. It preferably contains at least some naphtha. In this case, the first liquid may contain diethylene glycol monoethyl ether acetate.
　感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物における蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサは、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサであることが好ましい。 From the viewpoint of coating the photosensitive composition more uniformly, naphtha having an initial boiling point of 150 ° C. or more in the distillation property and an end point of distillation property of 290 ° C. or less in the photosensitive composition is the first in the distillation property. A naphtha having a boiling point of 150 ° C. or higher and an end point in distillation properties of 220 ° C. or lower is preferable.
　上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとからなる群から選択された少なくとも２種を含むことが好ましい。この場合には、上記第１，第２の液の混合性をより一層高めることができ、かつ感光性組成物をより一層均一に塗工できる。 The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), has an initial boiling point of 150 ° C. or more in distillation properties, and an end point in distillation properties of 290 ° C. It is preferable to include at least two selected from the group consisting of the following naphtha. In this case, the mixing property of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.
　上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとの３種を含んでいてもよい。 The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent (E), has an initial boiling point of 150 ° C. or more in distillation properties, and an end point in distillation properties of 290 ° C. You may include three types with the following naphtha.
　上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。この場合には、上記第１，第２の液の混合性をより一層高めることができ、かつ感光性組成物をより一層均一に塗工できる。 The first liquid contains, as a part of the organic solvent (E), at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties. It is preferable that at least 150 degreeC and the naphtha whose end point in distillation property is 290 degrees C or less are included. In this case, the mixing property of the first and second liquids can be further improved, and the photosensitive composition can be applied more uniformly.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むことが好ましい。この場合に、上記第１の液は、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサを含んでいてもよい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate. In this case, the first liquid may contain naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第１の液は、ジプロピレングリコールモノメチルエーテルを含むことが好ましい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 290 ° C. or lower in distillation properties. In this case, the first liquid preferably contains dipropylene glycol monomethyl ether.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第１の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第１の液は、ジエチレングリコールモノエチルエーテルアセテートを含んでいてもよい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the first liquid is used as a part of the organic solvent (E). It is preferable to contain at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. In this case, the first liquid may contain diethylene glycol monoethyl ether acetate.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記感光性組成物が、上記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、上記第１の液における蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサは、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサであることが好ましい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the photosensitive composition may be dipropylene glycol monomethyl ether as the organic solvent. And diethylene glycol monoethyl ether acetate and at least two selected from the group consisting of naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Distillation properties in the first liquid The naphtha having an initial boiling point of 150 ° C. or higher and an end point in distillation properties of 290 ° C. or lower is preferably a naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower.
　上記第１の液は、ジエチレングリコールモノエチルエーテルアセテートを含んでいなくてもよい。 The first liquid may not contain diethylene glycol monoethyl ether acetate.
　上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとからなる群から選択された少なくとも２種を含んでいてもよい。 In the second liquid, as part of the organic solvent (E), dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, the initial boiling point in distillation properties is 150 ° C. or higher, and the end point in distillation properties is 220 ° C. It may contain at least two kinds selected from the group consisting of the following naphtha.
　上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエチルエーテルアセテートと、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとの３種を含んでいてもよい。 The second liquid is diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether as part of the organic solvent (E), the initial boiling point in the distillation property is 150 ° C. or higher, and the end point in the distillation property is 220 ° C. You may include three types with the following naphtha.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエチルエーテルアセテートと、ジプロピレングリコールモノメチルエーテルとを少なくとも含むことが好ましい。この場合に、上記第２の液は、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサを含んでいてもよい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the second liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether. In this case, the second liquid may contain naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 220 ° C. or lower in distillation properties.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第２の液は、ジプロピレングリコールモノメチルエーテルを含むことが好ましい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the second liquid is used as a part of the organic solvent (E). It is preferable to contain at least diethylene glycol monoethyl ether acetate and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point of 220 ° C. or lower in distillation properties. In this case, the second liquid preferably contains dipropylene glycol monomethyl ether.
　上記第１，第２の液の混合性をより一層高め、かつ感光性組成物をより一層均一に塗工する観点からは、上記第２の液は、上記有機溶剤（Ｅ）の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含むことが好ましい。この場合に、上記第２の液は、ジエチレングリコールモノエチルエーテルアセテートを含んでいてもよい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the second liquid is used as a part of the organic solvent (E). It is preferable to include at least dipropylene glycol monomethyl ether and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties. In this case, the second liquid may contain diethylene glycol monoethyl ether acetate.
　上記第２の液は、ジエチレングリコールモノエチルエーテルアセテートを含んでいなくてもよい。 The second liquid may not contain diethylene glycol monoethyl ether acetate.
　有機溶剤（Ｅ）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、有機溶剤（Ｅ）は適宜の含有量で使用可能である。混合後の感光性組成物１００重量％中、上記有機溶剤（Ｅ）の全含有量（上記有機溶剤（Ｅ１）と上記有機溶剤（Ｅ２）との合計の含有量）は、好ましくは１０重量％以上、より好ましくは１５重量％以上、好ましくは６０重量％以下、より好ましくは５０重量％以下である。 The content of the organic solvent (E) is not particularly limited. In consideration of the coating properties of the photosensitive composition, the organic solvent (E) can be used in an appropriate content. In 100% by weight of the photosensitive composition after mixing, the total content of the organic solvent (E) (the total content of the organic solvent (E1) and the organic solvent (E2)) is preferably 10% by weight. Above, more preferably 15% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.
　上記第１，第２の液の混合性をより一層良好にし、感光性組成物をより一層均一に塗工する観点からは、２液混合型の第１，第２の液全体において、上記第１の液に含まれている有機溶剤（Ｅ１）の含有量と上記第２の液に含まれている有機溶剤（Ｅ２）の含有量とは重量比で、１：９９～９９：１であることが好ましく、１：９～９：１であることがより好ましく、２：８～８：２であることが更に好ましく、３：７～７：３であることが特に好ましい。言い換えれば、混合後の感光性組成物において、該感光性組成物に含まれている上記有機溶剤（Ｅ）の全含有量１００重量％中、上記第１の液に含まれていた有機溶剤（Ｅ１）の含有量と、上記第２の液に含まれていた上記有機溶剤（Ｅ２）の含有量とは重量比で、１：９９～９９：１であることが好ましく、１：９～９：１であることがより好ましく、２：８～８：２であることが更に好ましく、３：７～７：３であることが特に好ましい。 From the viewpoint of further improving the mixing properties of the first and second liquids and more uniformly coating the photosensitive composition, the first and second liquids of the two-liquid mixed type are used in the first and second liquids as a whole. The content of the organic solvent (E1) contained in the first liquid and the content of the organic solvent (E2) contained in the second liquid are 1:99 to 99: 1 in a weight ratio. It is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and particularly preferably 3: 7 to 7: 3. In other words, in the photosensitive composition after mixing, the organic solvent (E) contained in the first liquid in a total content of 100% by weight of the organic solvent (E) contained in the photosensitive composition ( The weight ratio of the content of E1) and the content of the organic solvent (E2) contained in the second liquid is preferably 1:99 to 99: 1, and 1: 9 to 9 : 1 is more preferable, 2: 8 to 8: 2 is still more preferable, and 3: 7 to 7: 3 is particularly preferable.
　２液混合型の第１，第２の液全体１００重量％中並びに混合後の感光性組成物１００重量％中、ジエチレングリコールモノエチルエーテルアセテートの含有量は３０重量％以上であってもよい。上記第１の液１００重量％中、ジエチレングリコールモノエチルエーテルアセテートの含有量は５０重量％以下であってもよく、５５重量％以上であってもよい。 The content of diethylene glycol monoethyl ether acetate may be 30% by weight or more in 100% by weight of the whole of the first and second liquids of the two-component mixed type and 100% by weight of the photosensitive composition after mixing. In 100% by weight of the first liquid, the content of diethylene glycol monoethyl ether acetate may be 50% by weight or less, or 55% by weight or more.
　上記第１の液が２種の有機溶剤を含む場合に、及び上記第２の液が２種の有機溶剤を含む場合に、上記第１の液及び上記第２の液において、含有量が多い方の有機溶剤の含有量と含有量が少ない方の有機溶剤の含有量とは重量比で、１：９９～９９：１であることが好ましく、１：９～９：１であることがより好ましく、２：８～８：２であることが更に好ましく、３：７～７：３であることが特に好ましい。 When the first liquid contains two kinds of organic solvents, and when the second liquid contains two kinds of organic solvents, the first liquid and the second liquid have a large content. The content of the organic solvent and the content of the organic solvent having a lower content are preferably in a weight ratio of 1:99 to 99: 1, more preferably 1: 9 to 9: 1. Preferably, it is 2: 8 to 8: 2, more preferably 3: 7 to 7: 3.
　上記第１の液が３種の有機溶剤を含む場合に、及び上記第２の液が３種の有機溶剤を含む場合に、上記第１の液及び上記第２の液において、含有量が最も多い有機溶剤の含有量と含有量が２番目に多い有機溶剤の含有量とは重量比で、１：９９～９９：１であることが好ましく、１：９～９：１であることがより好ましく、２：８～８：２であることが更に好ましく、３：７～７：３であることが特に好ましい。この場合に、含有量が最も少ない有機溶剤の含有量の下限は特に限定されない。 When the first liquid contains three kinds of organic solvents and when the second liquid contains three kinds of organic solvents, the content of the first liquid and the second liquid is the highest. The content of the organic solvent having the largest amount and the content of the organic solvent having the second largest content are preferably 1:99 to 99: 1 by weight, more preferably 1: 9 to 9: 1. Preferably, it is 2: 8 to 8: 2, more preferably 3: 7 to 7: 3. In this case, the lower limit of the content of the organic solvent having the smallest content is not particularly limited.
　（他の成分）
　硬化性をより一層高めるために、上記感光性組成物は、カルボキシル基を有する重合性重合体（Ａ）とは異なる成分として、重合性単量体を含むことが好ましい。上記感光性組成物は、カルボキシル基を有する重合性重合体（Ａ）と重合性単量体との双方を含むことが好ましい。上記重合性単量体は重合性を有し、重合可能である。上記重合性単量体は特に限定されない。上記重合性単量体は、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。 (Other ingredients)
In order to further improve the curability, the photosensitive composition preferably contains a polymerizable monomer as a component different from the polymerizable polymer (A) having a carboxyl group. The photosensitive composition preferably contains both a polymerizable polymer (A) having a carboxyl group and a polymerizable monomer. The polymerizable monomer is polymerizable and can be polymerized. The polymerizable monomer is not particularly limited. As for the said polymerizable monomer, only 1 type may be used and 2 or more types may be used together.
　上記重合性単量体は、重合性不飽和基含有単量体であることが好ましい。上記重合性単量体における重合性不飽和基としては、例えば、（メタ）アクリロイル基及びビニルエーテル基などの重合性不飽和二重結合を有する官能基が挙げられる。中でも、レジスト膜の架橋密度を高めることができるため、（メタ）アクリロイル基が好ましい。 The polymerizable monomer is preferably a polymerizable unsaturated group-containing monomer. Examples of the polymerizable unsaturated group in the polymerizable monomer include functional groups having a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl ether group. Among these, a (meth) acryloyl group is preferable because the crosslinking density of the resist film can be increased.
　上記重合性不飽和基含有単量体は、（メタ）アクリロイル基を有する化合物であることが好ましい。上記（メタ）アクリロイル基を有する化合物としては、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコールもしくはプロピレングリコールなどのグリコールのジ（メタ）アクリレート変性物や、多価アルコール、多価アルコールのエチレンオキサイド付加物もしくは多価アルコールのプロピレンオキサイド付加物の多価（メタ）アクリレート変性物や、フェノール、フェノールのエチレンオキサイド付加物もしくはフェノールのプロピレンオキサイド付加物の（メタ）アクリレート変性物や、グルセリンジグリシジルエーテルもしくはトリメチロールプロパントリグリシジルエーテルなどのグリシジルエーテルの（メタ）アクリレート変性物や、メラミン（メタ）アクリレートが挙げられる。 The polymerizable unsaturated group-containing monomer is preferably a compound having a (meth) acryloyl group. Examples of the compound having the (meth) acryloyl group include a di (meth) acrylate modified product of glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, polyhydric alcohol, and ethylene oxide adduct of polyhydric alcohol. Or a polyhydric (meth) acrylate modified product of a propylene oxide adduct of a polyhydric alcohol, a (meth) acrylate modified product of phenol, an ethylene oxide adduct of phenol or a propylene oxide adduct of phenol, glycerin diglycidyl ether or (Meth) acrylate modified products of glycidyl ether such as trimethylolpropane triglycidyl ether and melamine (meth) acrylate are exemplified.
　上記多価アルコールとしては、例えば、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、ジペンタエリスリトール及びトリス－ヒドロキシエチルイソシアヌレートが挙げられる。上記フェノールの（メタ）アクリレートとしては、例えば、フェノキシ（メタ）アクリレート及びビスフェノールＡのジ（メタ）アクリレート変性物が挙げられる。 Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate. Examples of the (meth) acrylate of phenol include phenoxy (meth) acrylate and di (meth) acrylate modified products of bisphenol A.
　「（メタ）アクリロイル」は、アクリロイルとメタクリロイルとを意味する。「（メタ）アクリル」は、アクリルとメタクリルとを意味する。「（メタ）アクリレート」は、アクリレートとメタクリレートとを意味する。 “(Meth) acryloyl” means acryloyl and methacryloyl. “(Meth) acryl” means acrylic and methacrylic. “(Meth) acrylate” means acrylate and methacrylate.
　上記重合性単量体が含まれる場合には、該重合性単量体と上記カルボキシル基を有する重合性重合体（Ａ）との合計１００重量％中、上記重合性単量体の含有量は好ましくは５重量％以上、好ましくは５０重量％以下である。上記重合性単量体の含有量が上記下限以上及び上記上限以下であると、感光性組成物を十分に硬化させることができる。さらに、レジスト膜の架橋密度が適度になり、十分な解像度を得ることができ、かつレジスト膜が黄変しにくくなる。 When the polymerizable monomer is contained, the content of the polymerizable monomer is 100% by weight in total of the polymerizable monomer and the polymerizable polymer (A) having a carboxyl group. Preferably it is 5 weight% or more, Preferably it is 50 weight% or less. A photosensitive composition can fully be hardened as content of the said polymerizable monomer is more than the said minimum and below the said upper limit. Furthermore, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is hardly yellowed.
　高温に晒されたときにソルダーレジスト膜が黄変するおそれを小さくするために、上記感光性組成物は、酸化防止剤を含有することが好ましい。上記酸化防止剤は、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、上記酸化防止剤は、フェノール系酸化防止剤、リン系酸化防止剤及び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１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、上記酸化防止剤は、フェノール系酸化防止剤であることが好ましい。すなわち、上記感光性組成物は、フェノール系酸化防止剤を含むことが好ましい。 In order to reduce the possibility that the solder resist film will turn yellow when exposed to high temperatures, the photosensitive composition preferably contains an antioxidant. The antioxidant preferably has a Lewis basic site. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Is preferred. From the viewpoint of further suppressing the yellowing of the resist film, the antioxidant is preferably a phenolic antioxidant. That is, the photosensitive composition preferably contains 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、及び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、及びアデカスタブ　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）、及びＳｕｍｉｌｉｚｅｒ　ＧＰ（以上、いずれも住友化学工業社製）、ＨＯＳＴＡＮＯＸ　Ｏ１０、ＨＯＳＴＡＮＯＸ　Ｏ１６、ＨＯＳＴＡＮＯＸ　Ｏ１４、及び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、及びアンテージ　Ｗ５００（以上、いずれも川口化学工業社製）、並びにＳＥＥＮＯＸ　２２４Ｍ、及び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, and IRGANOX 295 (all of which are manufactured by Ciba Japan), ADK STAB 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, and ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, and Sumizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and S milizer GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all of which are manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (above, both are manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, and SEENOX 326M (all are manufactured by Sipro Kasei Co., Ltd.).
　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及び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、アデカスタブ　ＰＥＰ－４Ｃ、アデカスタブ　ＰＥＰ－８、アデカスタブ　ＰＥＰ－２４Ｇ、アデカスタブ　ＰＥＰ－３６、アデカスタブ　ＨＰ－１０、アデカスタブ　２１１２、アデカスタブ　２６０、アデカスタブ　５２２Ａ、アデカスタブ　１１７８、アデカスタブ　１５００、アデカスタブ　Ｃ、アデカスタブ　１３５Ａ、アデカスタブ　３０１０、及びアデカスタブ　ＴＰＰ（以上、いずれもＡＤＥＫＡ社製）、サンドスタブ　Ｐ－ＥＰＱ、及びホスタノックス　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、及び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 phosphoric antioxidants include ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, and ADK STAB 1178 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, and ADK STAB TPP (all of which are manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all of which are manufactured by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 Re also be mentioned Johoku Chemical Industry 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－トリアジン及び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- And diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.
　上記カルボキシル基を有する重合性重合体（Ａ）１００重量部に対して、上記酸化防止剤の含有量は好ましくは０．１重量部以上、より好ましくは５重量部以上、好ましくは３０重量部以下、より好ましくは１５重量部以下である。上記酸化防止剤の含有量が上記下限以上及び上限以下であると、耐熱黄変性により一層優れたレジスト膜を形成できる。 The content of the antioxidant is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts by weight or less with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. More preferably, it is 15 parts by weight or less. When the content of the antioxidant is not less than the above lower limit and not more than the upper limit, a more excellent resist film can be formed by heat yellowing.
　また、上記感光性組成物は、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。 In addition, the photosensitive composition 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, a surface modification agent. A quality agent, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor may be included.
　上記感光性組成物は、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 above-mentioned photosensitive composition can be prepared, for example, by stirring and mixing the blending components and then uniformly mixing with three rolls.
　上記感光性組成物を硬化させるために用いられる光源としては、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。上記光源としては、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及び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 .
　（ＬＥＤデバイス）
　本発明に係る２液混合型の第１，第２の液は、ＬＥＤデバイスのレジスト膜を形成するために好適に用いられ、ソルダーレジスト膜を形成するためにより好適に用いられる。本発明に係る２液混合型の第１，第２の液は、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好ましい。 (LED device)
The two-liquid mixed type first and second liquids according to the present invention are preferably used for forming a resist film of an LED device, and more preferably used for forming a solder resist film. The two-liquid mixed type first and second liquids according to the present invention are preferably resist compositions, and are preferably solder resist compositions.
　本発明に係るプリント配線板の製造方法は、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プリント配線板の製造方法である。該レジスト膜が、本発明に係る２液混合型の第１，第２の液により形成されている。 A method for manufacturing a printed wiring board according to the present invention is a method for manufacturing a printed wiring board comprising a printed wiring board main body having a circuit on its surface and a resist film laminated on the surface of the printed wiring board main body provided with the circuit. Is the method. The resist film is formed of a two-liquid mixed type first and second liquid according to the present invention.
　図１に、本発明の一実施形態に係る２液混合型の第１，第２の液を用いて形成されたソルダーレジスト膜を有するＬＥＤデバイスの一例を模式的に部分切欠正面断面図で示す。 FIG. 1 schematically shows an example of an LED device having a solder resist film formed using a two-liquid mixed type first and second liquid according to an embodiment of the present invention in a partially cutaway front sectional view. .
　図１に示すＬＥＤデバイス１では、基板２の上面２ａに、２液混合型の第１，第２の液により形成されたレジスト膜３が積層されている。レジスト膜３は、パターン膜である。よって、基板２の上面２ａの一部の領域では、レジスト膜３は形成されていない。レジスト膜３が形成されていない部分の基板２の上面２ａには、電極４ａ，４ｂが設けられている。基板２は、プリント配線板本体であることが好ましい。 In the LED device 1 shown in FIG. 1, a resist film 3 formed of a two-liquid mixed type first and second liquid is laminated on an upper surface 2a of a substrate 2. The resist film 3 is a pattern film. Therefore, the resist film 3 is not formed in a part of the upper surface 2 a of the substrate 2. Electrodes 4a and 4b are provided on the upper surface 2a of the substrate 2 where the resist film 3 is not formed. The substrate 2 is preferably a printed wiring board body.
　レジスト膜３の上面３ａに、ＬＥＤチップ７が積層されている。レジスト膜３を介して、基板２上にＬＥＤチップ７が積層されている。ＬＥＤチップ７の下面７ａの外周縁には、端子８ａ，８ｂが設けられている。はんだ９ａ，９ｂにより、端子８ａ，８ｂが電極４ａ，４ｂと電気的に接続されている。この電気的な接続により、ＬＥＤチップ７に電力を供給できる。 The LED chip 7 is laminated on the upper surface 3 a of the resist film 3. An LED chip 7 is laminated on the substrate 2 via the resist film 3. Terminals 8 a and 8 b are provided on the outer peripheral edge of the lower surface 7 a of the LED chip 7. The terminals 8a and 8b are electrically connected to the electrodes 4a and 4b by the solder 9a and 9b. By this electrical connection, power can be supplied to the LED chip 7.
　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.
　実施例及び比較例では、以下の材料１）～１８）を用いた。 In the examples and comparative examples, the following materials 1) to 18) were used.
　１）アクリルポリマー１（カルボキシル基を有する重合性重合体、下記合成例１で得られたアクリルポリマー１） 1) Acrylic polymer 1 (polymer having a carboxyl group, acrylic polymer 1 obtained in Synthesis Example 1 below)
　（合成例１）
　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、溶剤であるエチルカルビトールアセテートと、触媒である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、重量平均分子量１５０００、二重結合当量１０００のカルボキシル基含有樹脂を５０重量％（不揮発分）含む溶液を得た。以下、この溶液をアクリルポリマー１と呼ぶ。 (Synthesis Example 1)
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. in a nitrogen atmosphere, and methacrylic. A monomer in which acid and methyl methacrylate were mixed 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 wt% (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 60 mg KOH / g, a weight average molecular weight of 15000, and a double bond equivalent of 1000. Hereinafter, this solution is referred to as acrylic polymer 1.
　２）アクリルポリマー２（カルボキシル基を有する重合性重合体、下記合成例２で得られたアクリルポリマー２） 2) Acrylic polymer 2 (polymerizable polymer having a carboxyl group, acrylic polymer 2 obtained in Synthesis Example 2 below)
　（合成例２）
　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」、新日鐵化学社製）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％（不揮発分）含む溶液を得た。以下、この溶液をアクリルポリマー２と呼ぶ。 (Synthesis Example 2)
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 Nippon Steel Chemical 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. A solution containing 65% by weight (non-volatile content) of a carboxyl group-containing resin having was obtained. Hereinafter, this solution is called acrylic polymer 2.
　３）ＤＰＨＡ（アクリルモノマー、ジペンタエリスリトールヘキサアクリレート、比重１．１） 3) DPHA (acrylic monomer, dipentaerythritol hexaacrylate, specific gravity 1.1)
　４）ＴＭＰＴＡ（アクリルモノマー、トリメチロールプロパントリアクリレート、比重１．１） 4) TMPTA (acrylic monomer, trimethylolpropane triacrylate, specific gravity 1.1)
　５）ＴＰＯ（光ラジカル発生剤である光重合開始剤、ＢＡＳＦジャパン社製） 5) TPO (photopolymerization initiator that is a photo radical generator, manufactured by BASF Japan)
　６）イルガキュア８１９（光ラジカル発生剤である光重合開始剤、ＢＡＳＦジャパン社製） 6) Irgacure 819 (photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan Ltd.)
　７）８２８（ビスフェノールＡ型エポキシ樹脂、三菱化学社製、比重１．２） 7) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)
　８）８０６（ビスフェノールＦ型エポキシ樹脂、三菱化学社製、比重１．２） 8) 806 (bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)
　９）ＣＲ－５０（酸化チタン、石原産業社製、塩素法により製造されたルチル型酸化チタン） 9) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the chlorine method)
　１０）Ｒ－８３０（酸化チタン、石原産業社製、硫酸法により製造されたルチル型酸化チタン） 10) R-830 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the sulfuric acid method)
　１１）エチルカルビトールアセテート（ジエチレングリコールモノエチルエーテルアセテート、ダイセル化学社製、双極子モーメント１Ｄｅｂｙｅ以上、比重１．０） 11) Ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel Chemical Industries, dipole moment 1 Debye or more, specific gravity 1.0)
　１２）ソルベッソ１５０（ナフサ、エクソンモービル社製、蒸留性状における初留点１８９℃、蒸留性状における終点２１０℃） 12) Solvesso 150 (Naphtha, ExxonMobil Corporation, initial boiling point 189 ° C. in distillation properties, end point 210 ° C. in distillation properties)
　１３）ソルベッソ１００（ナフサ、エクソンモービル社製、蒸留性状における初留点１６５℃、蒸留性状における終点１７４℃） 13) Solvesso 100 (naphtha, manufactured by ExxonMobil, initial boiling point 165 ° C. in distillation properties, end point 174 ° C. in distillation properties)
　１４）ジプロピレングリコールモノメチルエーテル（日本乳化剤社製） 14) Dipropylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.)
　１５）ジメチルプロピレンジグリコール（日本乳化剤社製） 15) Dimethylpropylene diglycol (manufactured by Nippon Emulsifier Co., Ltd.)
　１６）ジエチルジグリコール（日本乳化剤社製） 16) Diethyl diglycol (manufactured by Nippon Emulsifier Co., Ltd.)
　１７）ソルベッソ２００（ナフサ、エクソンモービル社製、蒸留性状における初留点２３０℃、蒸留性状における終点２８３℃） 17) Solvesso 200 (Naphtha, ExxonMobil Corporation, initial boiling point 230 ° C. in distillation properties, end point 283 ° C. in distillation properties)
　１８）トルエン（エクソンモービル社製） 18) Toluene (made by ExxonMobil)
　（実施例１）
　合成例１で得られたアクリルポリマー１を１５ｇと、ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート）５ｇと、ＴＰＯ（光ラジカル発生剤である光重合開始剤、ＢＡＳＦジャパン社製）２ｇと、ＣＲ－５０（酸化チタン、石原産業社製）４０ｇと、ソルベッソ１５０（ナフサ、エクソンモービル社製）２５ｇ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、第１の液を得た。 Example 1
15 g of the acrylic polymer 1 obtained in Synthesis Example 1, 5 g of DPHA (dipentaerythritol hexaacrylate), 2 g of TPO (a photopolymerization initiator that is a photoradical generator, manufactured by BASF Japan), and CR-50 ( 40 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) and 25 g of Solvesso 150 (naphtha, manufactured by ExxonMobil Corp.) are mixed and mixed for 3 minutes with a blender (Nentaro SP-500, manufactured by Shinky Corp.) The mixture was obtained by a roll to obtain a mixture. Thereafter, the obtained mixture was degassed for 3 minutes using SP-500 to obtain a first liquid.
　８２８（ビスフェノールＡ型エポキシ樹脂、三菱化学社製）８ｇと、エチルカルビトールアセテート（ジエチレングリコールモノエチルエーテルアセテート、ダイセル化学社製）５ｇ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、第２の液を得た。 8 g of 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) and 5 g of ethyl carbitol acetate (diethylene glycol monoethyl ether acetate, manufactured by Daicel Chemical Co., Ltd.) are blended, and a mixer (Nentaro SP-500, manufactured by Shinky Corp.) ) For 3 minutes and then mixed with 3 rolls to obtain a mixture. 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２～４９、参考例１～１１及び比較例１～１９）
　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１～８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、第１，第２の液を有する２液混合型の第１，第２の液（混合前の感光性組成物）を得た。 (Examples 2 to 49, Reference Examples 1 to 11 and Comparative Examples 1 to 19)
The first and second liquids were the same as in Example 1 except that the types and amounts of the materials used in the first liquid and the second liquid were changed as shown in Tables 1 to 8 below. A two-liquid mixed type first and second liquid (photosensitive composition before mixing) was obtained.
　（評価）
　２液の混合性：
　第１の液と第２の液とを、１Ｌの丸型のプラスチックス容器（近畿容器社製ＢＨＳ－１２００）に入れ、メッシュ社製自動インキ練機により、５０ｒｐｍで１０秒間攪拌したレジスト材料（混合後の感光性組成物）を作製した。第１の液と第２の液とを、１Ｌの丸型のプラスチックス容器（近畿容器社製ＢＨＳ－１２００）に入れ、メッシュ社製自動インキ練機により、５０ｒｐｍで２０秒間攪拌したレジスト材料（混合後の感光性組成物）を作製した。第１の液と第２の液とを、１Ｌの丸型のプラスチックス容器（近畿容器社製ＢＨＳ－１２００）に入れ、メッシュ社製自動インキ練機により、５０ｒｐｍで１分間攪拌したレジスト材料（混合後の感光性組成物）を作製した。さらに、第１の液と第２の液とを、１Ｌの丸型のプラスチックス容器（近畿容器社製ＢＨＳ－１２００）に入れ、メッシュ社製自動インキ練機により、５０ｒｐｍで５分間攪拌したレジスト材料（混合後の感光性組成物）を作製した。 (Evaluation)
Mixability of two liquids:
The first liquid and the second liquid are placed in a 1 L round plastic container (BHS-1200 manufactured by Kinki Container Co., Ltd.), and the resist material is stirred for 10 seconds at 50 rpm by an automatic ink kneader manufactured by Mesh Co., Ltd. A photosensitive composition after mixing) was prepared. The first liquid and the second liquid are placed in a 1 L round plastic container (BHS-1200 manufactured by Kinki Container Co., Ltd.), and the resist material is stirred for 20 seconds at 50 rpm by a mesh automatic ink kneader ( A photosensitive composition after mixing) was prepared. The first liquid and the second liquid are placed in a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.), and the resist material is stirred for 1 minute at 50 rpm by an automatic ink kneader manufactured by Mesh Co., Ltd. A photosensitive composition after mixing) was prepared. Further, the first liquid and the second liquid are put into a 1 L round plastic container (BHS-1200, manufactured by Kinki Container Co., Ltd.), and the resist is stirred for 5 minutes at 50 rpm by an automatic ink kneader manufactured by Mesh Co. A material (photosensitive composition after mixing) was prepared.
　また、表面に銅箔が貼り付けられている、１００×１００ｍｍのＦＲ－４基板を用意した。撹拌直後のレジスト材料を、上記ＦＲ－４基板の銅箔が貼り付けられている面に、スクリーン印刷により塗布して、レジスト材料層を形成した。基板上のレジスト材料層の外観を目視で観察した。 Also, a 100 × 100 mm FR-4 substrate with a copper foil attached to the surface was prepared. The resist material immediately after stirring was applied to the surface of the FR-4 substrate on which the copper foil was attached by screen printing to form a resist material layer. The appearance of the resist material layer on the substrate was visually observed.
　第１，第２の液の混合性を下記の判定基準で判定した。 The mixing property of the first and second liquids was determined according to the following criteria.
　［第１，第２の液の混合性の判定基準］
　Ａ：１０秒間撹拌したレジスト材料、２０秒間撹拌したレジスト材料、１分間撹拌したレジスト材料及び５分間撹拌したレジスト材料のいずれを用いた場合でも、レジスト材料層は均一であった [Judgment Criteria for Mixability of First and Second Liquids]
A: The resist material layer was uniform regardless of whether the resist material stirred for 10 seconds, the resist material stirred for 20 seconds, the resist material stirred for 1 minute, or the resist material stirred for 5 minutes was used.
　Ｂ：１０秒間撹拌したレジスト材料を用いた場合には、レジスト材料層にわずかにスジ状のむらがみられたものの、２０秒間撹拌したレジスト材料、１分間撹拌したレジスト材料及び５分間撹拌したレジスト材料を用いた場合には、レジスト材料層は均一であった B: When a resist material stirred for 10 seconds was used, the resist material layer was slightly streaked, but the resist material stirred for 20 seconds, the resist material stirred for 1 minute, and the resist material stirred for 5 minutes The resist material layer was uniform.
　Ｃ：１０秒間撹拌したレジスト材料及び２０秒間撹拌したレジスト材料を用いた場合には、レジスト材料層にわずかにスジ状のむらがみられたものの、１分間撹拌したレジスト材料及び５分間撹拌したレジスト材料を用いた場合には、レジスト材料層は均一であった C: When a resist material stirred for 10 seconds and a resist material stirred for 20 seconds were used, although the resist material layer had slight streak-like unevenness, the resist material stirred for 1 minute and the resist material stirred for 5 minutes The resist material layer was uniform.
　Ｄ：１０秒間撹拌したレジスト材料、２０秒間撹拌したレジスト材料及び１分間撹拌したレジスト材料を用いた場合には、レジスト材料層にわずかにスジ状のむらがみられたものの、５分間撹拌したレジスト材料を用いた場合には、レジスト材料層は均一であった D: When resist material stirred for 10 seconds, resist material stirred for 20 seconds, and resist material stirred for 1 minute were used, although the resist material layer had slight streaky irregularities, the resist material stirred for 5 minutes The resist material layer was uniform.
　Ｅ：１０秒間撹拌したレジスト材料、２０秒間撹拌したレジスト材料、１分間撹拌したレジスト材料及び５分間撹拌したレジスト材料のいずれを用いた場合でも、レジスト材料層にスジ状のむらがみられた E: Streak-like unevenness was observed in the resist material layer when any of the resist material stirred for 10 seconds, the resist material stirred for 20 seconds, the resist material stirred for 1 minute, and the resist material stirred for 5 minutes was used.
　結果を下記の表１～８に示す。下記の表１～８において、配合された液の種別における「（１）」は第１の液を表し、「（２）」は第２の液を表す。なお、上記第１，第２の液の混合性の評価後に、基板上のレジスト材料層を硬化させることで、レジスト膜を得ることができた。 The results are shown in Tables 1 to 8 below. In Tables 1 to 8 below, “(1)” in the type of the blended liquid represents the first liquid, and “(2)” represents the second liquid. In addition, the resist film was able to be obtained by hardening the resist material layer on a board | substrate after evaluation of the mixing property of the said 1st, 2nd liquid.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
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
　なお、実施例５と実施例２９と実施例３３との２液の混合性の評価結果はいずれも「Ａ」であるが、実施例５と実施例２９の方が、実施例３３よりもより一層短時間で、感光性組成物が均一に混合された。実施例３０と実施例３１と実施例３４との２液の混合性の評価結果はいずれも「Ａ」であるが、実施例３０と実施例３１の方が、実施例３４よりもより一層短時間で、感光性組成物が均一に混合された。実施例３５と実施例３７と実施例３９との２液の混合性の評価結果はいずれも「Ａ」であるが、実施例３５と実施例３７の方が、実施例３９よりもより一層短時間で、感光性組成物が均一に混合された。 Note that the evaluation results of the mixing properties of the two liquids of Example 5, Example 29, and Example 33 are all “A”, but Example 5 and Example 29 are more preferable than Example 33. In a shorter time, the photosensitive composition was uniformly mixed. The evaluation results of the mixing properties of the two liquids of Example 30, Example 31 and Example 34 are all “A”, but Example 30 and Example 31 are much shorter than Example 34. Over time, the photosensitive composition was uniformly mixed. The evaluation results of the mixing properties of the two liquids of Example 35, Example 37, and Example 39 are all “A”, but Example 35 and Example 37 are much shorter than Example 39. Over time, the photosensitive composition was uniformly mixed.
　１…ＬＥＤデバイス
　２…基板
　２ａ…上面
　３…レジスト膜
　３ａ…上面
　４ａ，４ｂ…電極
　７…ＬＥＤチップ
　７ａ…下面
　８ａ，８ｂ…端子
　９ａ，９ｂ…はんだ DESCRIPTION OF SYMBOLS 1 ... LED device 2 ... Board | substrate 2a ... Upper surface 3 ... Resist film 3a ... Upper surface 4a, 4b ... Electrode 7 ... LED chip 7a ... Lower surface 8a, 8b ... Terminal 9a, 9b ... Solder

Claims (21)

  1. 　混合物である感光性組成物を得るための２液混合型の第１，第２の液であり、該２液混合型の第１，第２の液は該第１，第２の液が混合される前の液であり、
    　前記第１，第２の液が混合された混合物である感光性組成物が全体で、カルボキシル基を有する重合性重合体と、光重合開始剤と、環状エーテル基を有する化合物と、酸化チタンと、有機溶剤とを含み、
    　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記重合性重合体を含み、かつ前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含み、
    　前記第２の液が、前記環状エーテル基を有する化合物を含み、かつ前記有機溶剤の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含み、
    　前記第１の液が、前記光重合開始剤を含むか、前記酸化チタンを含むか、又は前記光重合開始剤と前記酸化チタンとの双方を含み、
    　前記第１の液が前記光重合開始剤を含まない場合には前記第２の液が前記光重合開始剤を含み、前記第１の液が前記酸化チタンを含まない場合には前記第２の液が前記酸化チタンを含む、２液混合型の第１，第２の液。     Two-liquid mixed type first and second liquids for obtaining a photosensitive composition as a mixture, and the two-liquid mixed type first and second liquids are mixed by the first and second liquids. The liquid before being
    The photosensitive composition which is a mixture in which the first and second liquids are mixed as a whole, a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, titanium oxide, Including organic solvents,
    The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. Including at least two selected,
    The first liquid contains the polymerizable polymer, and, as a part of the organic solvent, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point in distillation properties of 150 ° C. or more, in distillation properties Including at least one selected from the group consisting of naphtha having an end point of 290 ° C. or lower,
    The second liquid contains the compound having the cyclic ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point in distillation properties of 150 ° C. or higher, Including at least one selected from the group consisting of naphtha whose end point in distillation properties is 220 ° C. or lower,
    The first liquid contains the photopolymerization initiator, contains the titanium oxide, or contains both the photopolymerization initiator and the titanium oxide,
    When the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, the second liquid A two-liquid mixed type first and second liquid, wherein the liquid contains the titanium oxide.
  2. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含む、請求項１に記載の２液混合型の第１，第２の液。 The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and 290 ° C. or lower in distillation properties. The two-liquid mixed type first and second liquids according to claim 1, comprising at least two kinds selected from the group consisting of:
  3. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む、請求項１に記載の２液混合型の第１，第２の液。 The first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate as a part of the organic solvent, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties of 150 ° C. The two-liquid mixed type first and second liquids according to claim 1, comprising at least naphtha having an end point in distillation properties of 290 ° C or lower.
  4. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む、請求項１に記載の２液混合型の第１，第２の液。 The first liquid contains at least dipropylene glycol monomethyl ether as a part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. Item 2. A two-component mixed first and second liquid according to item 1.
  5. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含む、請求項１に記載の２液混合型の第１，第２の液。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 220 ° C. or less. The two-liquid mixed type first and second liquids according to claim 1, comprising at least two kinds selected from the group consisting of:
  6. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含む、請求項１に記載の２液混合型の第１，第２の液。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid contains dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate as a part of the organic solvent, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties of 150 ° C. or higher. The two-component mixed type first and second liquids according to claim 1, comprising at least naphtha whose end point in distillation properties is 220 ° C. or lower.
  7. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含む、請求項１に記載の２液混合型の第１，第２の液。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid contains at least dipropylene glycol monomethyl ether as a part of the organic solvent and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties. Item 2. A two-component mixed first and second liquid according to item 1.
  8. 　前記第１の液が前記光重合開始剤を含む、請求項１～７のいずれか１項に記載の２液混合型の第１，第２の液。 The two-liquid mixed type first and second liquid according to any one of claims 1 to 7, wherein the first liquid contains the photopolymerization initiator.
  9. 　前記第１の液が前記酸化チタンを含む、請求項１～７のいずれか１項に記載の２液混合型の第１，第２の液。 The two-liquid mixed type first and second liquid according to any one of claims 1 to 7, wherein the first liquid contains the titanium oxide.
  10. 　前記第１の液が前記光重合開始剤と前記酸化チタンとの双方を含む、請求項１～７のいずれか１項に記載の２液混合型の第１，第２の液。 The two-liquid mixed type first and second liquid according to any one of claims 1 to 7, wherein the first liquid contains both the photopolymerization initiator and the titanium oxide.
  11. 　前記第１，第２の液が混合された感光性組成物がソルダーレジスト組成物である、請求項１～７のいずれか１項に記載の２液混合型の第１，第２の液。 The two-component mixed type first and second liquids according to any one of claims 1 to 7, wherein the photosensitive composition in which the first and second liquids are mixed is a solder resist composition.
  12. 　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回路が設けられた表面に積層されたソルダーレジスト膜とを備えるプリント配線板の製造方法であって、
    　第１，第２の液を混合し、前記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物を得る工程と、
    　回路を表面に有するプリント配線板本体の回路が設けられた表面上に、前記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物を塗工して、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ソルダーレジスト膜を形成する工程とを備え、
    　前記第１，第２の液が混合されたソルダーレジスト組成物である感光性組成物が全体で、カルボキシル基を有する重合性重合体と、光重合開始剤と、環状エーテル基を有する化合物と、酸化チタンと、有機溶剤とを含み、
    　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記重合性重合体を含み、かつ前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも１種を含み、
    　前記第２の液が、前記環状エーテル基を有する化合物を含み、かつ前記有機溶剤の一部として、ジエチレングリコールモノエ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、及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも１種を含み、
    　前記第１の液が、前記光重合開始剤を含むか、前記酸化チタンを含むか、又は前記光重合開始剤と前記酸化チタンとの双方を含み、
    　前記第１の液が前記光重合開始剤を含まない場合には前記第２の液が前記光重合開始剤を含み、前記第１の液が前記酸化チタンを含まない場合には前記第２の液が前記酸化チタンを含む、プリント配線板の製造方法。     A printed wiring board main body having a circuit on its surface, and a printed wiring board manufacturing method comprising a solder resist film laminated on the surface on which the circuit of the printed wiring board main body is provided,
    Mixing the first and second liquids to obtain a photosensitive composition that is a solder resist composition in which the first and second liquids are mixed;
    Applying a photosensitive composition, which is a solder resist composition in which the first and second liquids are mixed, on the surface of the printed wiring board body having the circuit on the surface, the printed wiring Forming a solder resist film laminated on the surface of the board body provided with the circuit,
    The photosensitive composition which is a solder resist composition mixed with the first and second liquids as a whole, a polymerizable polymer having a carboxyl group, a photopolymerization initiator, a compound having a cyclic ether group, Including titanium oxide and an organic solvent,
    The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. Including at least two selected,
    The first liquid contains the polymerizable polymer, and, as a part of the organic solvent, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and an initial boiling point in distillation properties of 150 ° C. or more, in distillation properties Including at least one selected from the group consisting of naphtha having an end point of 290 ° C. or lower,
    The second liquid contains the compound having the cyclic ether group, and as part of the organic solvent, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and an initial boiling point in distillation properties of 150 ° C. or higher, Including at least one selected from the group consisting of naphtha whose end point in distillation properties is 220 ° C. or lower,
    The first liquid contains the photopolymerization initiator, contains the titanium oxide, or contains both the photopolymerization initiator and the titanium oxide,
    When the first liquid does not contain the photopolymerization initiator, the second liquid contains the photopolymerization initiator, and when the first liquid does not contain the titanium oxide, the second liquid A method for producing a printed wiring board, wherein the liquid contains the titanium oxide.
  13. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサからなる群から選択された少なくとも２種を含む、請求項１２に記載のプリント配線板の製造方法。 The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as a part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and 290 ° C. or lower in distillation properties. The manufacturing method of the printed wiring board of Claim 12 containing at least 2 sort (s) selected from the group which consists of.
  14. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む、請求項１２に記載のプリント配線板の製造方法。 The first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate as a part of the organic solvent, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties of 150 ° C. As mentioned above, the manufacturing method of the printed wiring board of Claim 12 including the naphtha whose end point in a distillation property is 290 degrees C or less.
  15. 　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２９０℃以下であるナフサとを少なくとも含む、請求項１２に記載のプリント配線板の製造方法。 The first liquid contains at least dipropylene glycol monomethyl ether as a part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 290 ° C. or less in distillation properties. Item 13. A method for producing a printed wiring board according to Item 12.
  16. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含む、請求項１２に記載のプリント配線板の製造方法。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid is dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as part of the organic solvent, and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point in distillation properties of 220 ° C. or less. The manufacturing method of the printed wiring board of Claim 12 containing at least 2 sort (s) selected from the group which consists of.
  17. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、ジエチレングリコールモノエチルエーテルアセテートとを少なくとも含むか、又はジエチレングリコールモノエチルエーテルアセテートと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含む、請求項１２に記載のプリント配線板の製造方法。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid contains at least dipropylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate as a part of the organic solvent, or diethylene glycol monoethyl ether acetate and an initial boiling point in distillation properties of 150 ° C. As mentioned above, the manufacturing method of the printed wiring board of Claim 12 including the naphtha whose end point in distillation property is 220 degrees C or less.
  18. 　前記感光性組成物が、前記有機溶剤として、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート及び蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサからなる群から選択された少なくとも２種を含み、
    　前記第１の液が、前記有機溶剤の一部として、ジプロピレングリコールモノメチルエーテルと、蒸留性状における初留点が１５０℃以上、蒸留性状における終点が２２０℃以下であるナフサとを少なくとも含む、請求項１２に記載のプリント配線板の製造方法。     The photosensitive composition is selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate as an organic solvent, and naphtha having an initial boiling point of 150 ° C. or higher in distillation properties and an end point in distillation properties of 220 ° C. or lower. Including at least two selected,
    The first liquid contains at least dipropylene glycol monomethyl ether as a part of the organic solvent and naphtha having an initial boiling point of 150 ° C. or more in distillation properties and an end point of 220 ° C. or less in distillation properties. Item 13. A method for producing a printed wiring board according to Item 12.
  19. 　前記第１の液が前記光重合開始剤を含む、請求項１２～１８のいずれか１項に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains the photopolymerization initiator.
  20. 　前記第１の液が前記酸化チタンを含む、請求項１２～１８のいずれか１項に記載のプリント配線板の製造方法。 The method for manufacturing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains the titanium oxide.
  21. 　前記第１の液が前記光重合開始剤と前記酸化チタンとの双方を含む、請求項１２～１８のいずれか１項に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to any one of claims 12 to 18, wherein the first liquid contains both the photopolymerization initiator and the titanium oxide.
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