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WO2020203074A1 - Low-temperature curable resin composition - Google Patents

Low-temperature curable resin composition Download PDF

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Publication number
WO2020203074A1
WO2020203074A1 PCT/JP2020/010051 JP2020010051W WO2020203074A1 WO 2020203074 A1 WO2020203074 A1 WO 2020203074A1 JP 2020010051 W JP2020010051 W JP 2020010051W WO 2020203074 A1 WO2020203074 A1 WO 2020203074A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
color filter
homopolymer
photoacid generator
manufactured
Prior art date
Application number
PCT/JP2020/010051
Other languages
French (fr)
Japanese (ja)
Inventor
陽介 大竹
安達　勲
崇洋 坂口
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to JP2021511311A priority Critical patent/JP7208593B2/en
Priority to CN202080024897.5A priority patent/CN113631586A/en
Priority to KR1020217028311A priority patent/KR102574725B1/en
Publication of WO2020203074A1 publication Critical patent/WO2020203074A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking

Definitions

  • the present invention relates to a resin composition used for forming a cured film formed on a lower layer and an upper layer of a color filter in a device provided with a color filter such as an image sensor and a display device.
  • the present invention relates to a low temperature curable resin composition capable of forming a cured film at a baking temperature not exceeding 110 ° C.
  • a transparent resin film such as a protective film or a flattening film is formed on the upper layer of the color filter for the purpose of protecting the color filter and smoothing the unevenness of the surface of the color filter.
  • a transparent resin film is also applied to the lower layer of the color filter for the purpose of improving the adhesion between the color filter and the base substrate and smoothing the unevenness caused by the presence of the circuit wiring part, the light-shielding film, the inner lens, etc. Is formed.
  • Compositions for forming such a transparent resin film are disclosed in, for example, Patent Documents 1 to 4.
  • a color resist of three colors of red, green and blue containing a pigment or a dye is generally used.
  • a color resist of the first color is applied, and exposure, development, and heat treatment are performed to form a color resist pattern of the first color.
  • the color resist patterns of the second color and the third color are formed in the same manner as the color resist pattern of the first color, and the color filter is formed.
  • the organic EL display device be manufactured by a process at a lower temperature than other devices.
  • a process at a lower temperature for example, as disclosed in Patent Document 5, in order to maintain the characteristics of the organic EL element, it is required not to apply a temperature higher than 110 ° C. Therefore, it is necessary that the transparent resin film formed on the upper and lower layers of the color filter can be formed by curing the resin composition at a temperature of 110 ° C. or lower.
  • the transparent resin film When a color filter is formed on the transparent resin film, the transparent resin film is required to have the characteristics of suppressing the generation of color resist residues as described above.
  • the transparent resin film formed from the conventional low-temperature curable material has a problem that it does not have a sufficient effect of suppressing the generation of residue of the color resist and a sufficient reliability as a permanent film.
  • the present invention has been made based on the above circumstances, and an object thereof is to be able to form a cured film having excellent solvent resistance and reliability at a temperature not exceeding 110 ° C., preferably 100 ° C. or lower. It is an object of the present invention to provide a resin composition capable of suppressing the generation of color resist residue when forming a color filter on the cured film and forming the cured film on the color filter. Another object of the present invention is to provide a method for manufacturing a device having a color filter, which has a color filter lower layer film and / or a color filter upper layer film having excellent solvent resistance and reliability.
  • the present invention uses homopolymers having a structural unit represented by the following formula (1), crosslinkable compounds having at least two alkoxyalkyl groups in one molecule, photoacid generators, surfactants, and organic solvents.
  • the content of the crosslinkable compound is 40% by mass to 60% by mass with respect to the content of the homopolymer, and the content of the photoacid generator is the content of the homopolymer and the crosslinkable compound.
  • the resin composition is at least 0.8% by mass based on the sum.
  • R 1 represents an alkyl group having at least one hydroxy group as a substituent and having 1 to 6 carbon atoms.
  • the acid generated from the photoacid generator is, for example, a superacid, and its acid dissociation constant pKa is, for example, smaller than -7.
  • the acid generated from the photoacid generator is, for example, Bronsted acid.
  • the photoacid generator is, for example, N- (trifluoromethanesulfonyloxy) -1,8-naphthalimide or a derivative thereof, or a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound.
  • Another aspect of the present invention is a step of applying the resin composition of the present invention on a substrate, the resin composition is prebaked at 75 ° C. to 110 ° C., exposed to near ultraviolet rays, and then posted at 75 ° C. to 110 ° C.
  • a method for manufacturing a device including a color filter which comprises a step of baking to form a color filter lower layer film and a step of forming a color filter on the color filter lower layer film using a color resist.
  • the method for producing a device provided with the color filter includes a step of applying the resin composition on the color filter, a prebaking of the resin composition at 75 ° C to 110 ° C, exposure to near ultraviolet rays, and then 75 ° C to It may further have a step of post-baking at 110 ° C. to form a color filter upper layer film.
  • the pre-baking and post-baking are preferably performed at 100 ° C. or lower.
  • the color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention has excellent chemical resistance, heat resistance and transparency.
  • the color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention can be used as a chemical solution such as an acid or alkaline solution or a solvent in the forming step thereof or the forming step of peripheral devices such as wiring.
  • the possibility of deterioration or damage of the element can be significantly reduced when the treatment is exposed, sputtering, and dry etching is performed.
  • the resin composition of the present invention is suitable as a material for forming a color filter lower layer film or a color filter upper layer film.
  • the present invention is a resin composition containing a specific homopolymer, a crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant and an organic solvent.
  • the details of each component will be described below.
  • the solid content of the resin composition of the present invention excluding the organic solvent is usually 0.01% by mass to 50% by mass.
  • the homopolymer contained in the resin composition of the present invention is a polymer having a structural unit represented by the above formula (1).
  • examples of the group represented by R 1 include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a dihydroxypropyl group, and a dihydroxybutyl group.
  • Examples of the compound (monomer) forming the structural unit represented by the formula (1) include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydrokipropyl methacrylate, 3-hydroxypropyl methacrylate, and 2,3-dihydroxy. Examples thereof include propyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3,4-dihydroxybutyl methacrylate, diethylene glycol monomethacrylate, and dipropylene glycol monomethacrylate.
  • a color filter is formed on a color filter lower layer film formed from the resin composition, and then the color filter is formed. The residue of the color resin generated on the lower layer film can be suppressed.
  • the weight average molecular weight of the homopolymer is usually 1,000 to 200,000, preferably 3,000 to 100,000.
  • the weight average molecular weight is a value obtained by gel permeation chromatography (GPC).
  • the content of the homopolymer in the resin composition of the present invention is usually 30% by mass to 99% by mass, preferably 60% by mass to 75% based on the content in the solid content of the resin composition. It is mass%.
  • the method for obtaining the homopolymer is not particularly limited, but in general, the compound (monomer) forming the structural unit represented by the formula (1) is placed in a solvent in the presence of a polymerization initiator. , Usually obtained by polymerizing at a temperature of 50 ° C to 120 ° C. The homopolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the resin composition of the present invention without being isolated in this state.
  • the homopolymer solution obtained as described above was put into a stirred poor solvent such as hexane, diethyl ether, toluene, methanol and water to reprecipitate the homopolymer, and the resulting precipitate was produced.
  • the homopolymer can be made into an oil or powder by decanting or filtering, washing if necessary, and then drying at room temperature or heating under normal pressure or reduced pressure. By such an operation, the polymerization initiator and the unreacted compound coexisting with the homopolymer can be removed.
  • the oily substance or powder of the homopolymer may be used as it is, or the oily substance or powder thereof may be redissolved in, for example, an organic solvent described later and used as a solution. ..
  • the crosslinkable compound contained in the resin composition of the present invention has at least two alkoxyalkyl groups in one molecule.
  • Examples of the crosslinkable compound include compounds having an alkoxyalkylated nitrogen atom.
  • Examples of the compound having an alkoxyalkylated nitrogen atom include (poly) methylolated melamine, (poly) methylolated glycoluryl, (poly) methylolated benzoguanamine, and (poly) methylolated urea in one molecule.
  • Examples of a nitrogen-containing compound having a plurality of active methylol groups in which at least one hydrogen atom of the hydroxy group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group can be mentioned. ..
  • the compound having an alkoxyalkylated nitrogen atom may be a mixture of a plurality of substituted compounds, and there is also a mixture containing an oligomer component which is partially self-condensed, and such a mixture is also used. be able to. More specifically, for example, hexamethoxymethylmelamine (manufactured by Nippon Cytec Industries Co., Ltd., CYMEL [registered trademark] 303), tetrabutoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd., CYMEL [registered trademark] 1170).
  • POWDERLINK series products methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., Nicarac [registered trademark] MW-30HM, MW-390, MW-100LM, MX-750LM), methylated urea resin ( Examples of Nikalac series products such as Nikalac (registered trademark) MX-270, MX-280, and MX-290) manufactured by Sanwa Chemical Co., Ltd. These crosslinkable compounds may be used alone or in combination of two or more.
  • the content of the crosslinkable compound in the resin composition of the present invention is preferably 40% by mass to 60% by mass based on the content of the homopolymer in the resin composition.
  • the content of the crosslinkable compound in the resin composition of the present invention is excessive or too small, it is observed on the color filter lower layer film after forming the color filter on the color filter lower layer film formed from the resin composition. There is a risk that the color resist residue will increase.
  • the photoacid generator contained in the resin composition of the present invention is a compound that generates a strong acid, preferably a superacid having an acid dissociation constant pKa of less than ⁇ 7, upon exposure.
  • the compound include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.
  • the onium salt compound examples include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butane sulfonate, diphenyliodonium perfluoro-n-octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-).
  • Iodonium salt compounds such as tert-butylphenyl) iodonium camphor sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, tri Phenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl ] Sulfonium hex
  • a sulfonium salt compound is preferable, and a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound is more preferable as a compound in which an acid is generated by exposure using i-ray (365 nm).
  • the sulfonylimide compound examples include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy)- 1,8-Naphthalimide, N- (trifluoromethanesulfonyloxy) -2-alkyl-1,8-naphthalimide, N- (trifluoromethanesulfonyloxy) -3-alkyl-1,8-naphthalimide and N- ( Examples thereof include trifluoromethanesulfonyloxy) -4-alkyl-1,8-naphthalimide.
  • N- (trifluoromethanesulfonyloxy) -1,8-naphthalimide and its derivatives are preferable to provide N- (trifluoromethan
  • disulfonyldiazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane.
  • ADEKA Arklus registered trademark
  • SP-701 SP-150, SP-170, SP-171 (all manufactured by ADEKA Corporation)
  • CPI registered trademark
  • -110P, -110B, -310B, -210S Same as -100P, Same as -101A, Same as -200K (all manufactured by Sun Apro Co., Ltd.)
  • the content of the photoacid generator in the resin composition of the present invention is usually 0.8% by mass to 20% based on the sum of the contents of the homopolymer and the crosslinkable compound in the resin composition. It is by mass, preferably 1.0% by mass to 15% by mass. If the content of the photoacid generator is too small in the resin composition of the present invention, the solvent resistance or reliability of the film formed from the resin composition may be insufficient.
  • the resin composition of the present invention contains a surfactant for the purpose of improving coatability.
  • the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxy.
  • Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Polysorbate fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
  • Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, Ftop [registered trademark] EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck [registered trademark] F-171 , F-173, R-30, R-40, R-40-LM (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431 (above, manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [Registered Trademarks] AG710, Surflon [Registered Trademarks] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), FTX-206D, FTX-212D, FTX- 218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-
  • the content of the surfactant in the resin composition of the present invention is usually 0.001% by mass to 3% by mass, preferably 0.01% by mass, based on the content of the homopolymer in the resin composition. % To 2% by mass, more preferably 0.1% by mass to 1% by mass.
  • Organic solvent contained in the resin composition of the present invention is not particularly limited as long as it dissolves the solid content contained in the resin composition.
  • organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether.
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether
  • propylene glycol monopropyl ether 2-heptanone, ethyl lactate, butyl lactate, cyclopentanone, cyclohexanone and ⁇ -butyrolactone are preferred.
  • the resin composition of the present invention may be a light stabilizer, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, an antifoaming agent, etc., as required, as long as the effects of the present invention are not impaired. Additives can be included.
  • the method for preparing the resin composition of the present invention is not particularly limited, and for example, a solution of a homopolymer having a structural unit represented by the above formula (1), a crosslinkable compound, a photoacid generator and a surfactant are specified. A method of dissolving in an organic solvent at the ratio of 1 to obtain a uniform solution can be mentioned. Further, at an appropriate stage of this preparation method, a method of further adding and mixing other additives, if necessary, can be mentioned.
  • a method for producing a color filter lower layer film or a color filter upper layer film using the resin composition of the present invention will be described.
  • Spinners, coaters, etc. on a substrate for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films, flattening films, color filters, organic EL elements, etc. are formed).
  • a coating film is formed by applying the resin composition of the present invention by an appropriate coating method of the above, and then prebaking using a heating means such as a hot plate or an oven. Subsequently, the coating film is exposed using an exposure machine.
  • the development treatment may be included after the resin composition is applied or prebaked.
  • the pre-baking and post-baking conditions are appropriately selected from a baking temperature of 75 ° C. to 110 ° C. and a baking time of 0.3 minutes to 60 minutes.
  • the post-bake may be processed in two or more steps.
  • near ultraviolet rays for example, i-rays
  • the thickness of the color filter lower layer film formed from the resin composition of the present invention is, for example, 0.06 ⁇ m to 0.5 ⁇ m, and the thickness of the color filter upper layer film formed from the resin composition of the present invention is, for example. It is 0.3 ⁇ m to 1.0 ⁇ m.
  • GPC device GPC system manufactured by Showa Denko KK (Shodex [registered trademark] GPC-101) Columns: Shodex® KD-800RH, KD-800RL, KD-803 and KD-805 Column temperature: 50 ° C Eluent: N, N-dimethylformamide [As additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) 30 mmol / L, and tetrahydrofuran ( THF) contains 10 ml / L.
  • LiBr ⁇ H 2 O lithium bromide-hydrate
  • o-phosphate phosphoric acid / anhydrous crystal
  • THF tetrahydrofuran
  • Example 2 8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator.
  • CPI-210S manufactured by Sun Appro Co., Ltd.
  • Megafuck [registered trademark] R-40 manufactured by DIC Co., Ltd.
  • 0.002 g propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl ether 26. It was dissolved in 3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 ⁇ m to prepare a resin composition.
  • Example 3 8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator.
  • CPI-110B manufactured by Sun Appro Co., Ltd.
  • Megafuck® R-40 manufactured by DIC Co., Ltd.
  • 0.002 g propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl ether 26. It was dissolved in 3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 ⁇ m to prepare a resin composition.
  • Example 4 8.0 g of the homopolymer solution obtained in Synthesis Example 1, 1.2 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator.
  • SP-606 manufactured by ADEKA Co., Ltd.
  • Megafuck [registered trademark] R-40 manufactured by DIC Co., Ltd.
  • 0.002 g propylene glycol monoethyl ether 15.8 g and propylene glycol monomethyl ether 30. It was dissolved in 9 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 ⁇ m to prepare a resin composition.
  • ⁇ Comparative example 1> 8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a thermoacid generator. 0.028 g of TAG2689 (manufactured by KING INDUSTRIES) and 0.002 g of Megafuck (registered trademark) R-40 (manufactured by DIC Co., Ltd.) are dissolved in 13.9 g of propylene glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. It was made into a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 ⁇ m to prepare a resin composition.
  • POWDERLINK® 1174 manufactured by Nippon Cytec Industries Co.,
  • POWDERLINK® 1174 manufactured by Nippon Cytec Industries Co., Ltd.
  • POWDERLINK® 1174 manufactured by Nippon Cytec Industries Co., Ltd.
  • SP-606 manufactured by ADEKA Co., Ltd.
  • Megafuck [registered trademark] R-40 manufactured by DIC Co., Ltd.
  • This comparative example is an example in which the content of the crosslinkable compound is too small.
  • SP-606 manufactured by ADEKA Co., Ltd.
  • Megafuck [registered trademark] R-40 manufactured by DIC Co., Ltd.
  • This comparative example is an example in which the content of the crosslinkable compound is excessive.
  • SP-606 manufactured by ADEKA Co., Ltd.
  • Megafuck [registered trademark] R-40 manufactured by DIC Co., Ltd.
  • This comparative example is an example in which the content of the crosslinkable compound is too small.
  • TMAH tetramethylammonium hydroxide
  • the film thickness change rate was calculated from the following formula, and was evaluated as “x” when the film thickness change rate exceeded 5% and as “ ⁇ ” when it was 5% or less.
  • the evaluation results are shown in Table 1. [1- (Film thickness after test / Film thickness before test)] x 100 (%)
  • a photoradical polymerizable pigment-dispersed red color resist solution containing Pigment Red 177 was applied and baked on a hot plate at 100 ° C. for 1 minute to form a red color resist film having a thickness of 0.5 ⁇ m.
  • the film formed from the resin composition of the present invention was highly solvent resistant and highly transparent. Further, on the film formed from the resin composition of the present invention, the residue of the color resist was small, and the film formed from the resin composition of the present invention was excellent in the effect of suppressing the generation of the residue of the color resist. ..
  • the film formed from the resin composition prepared in Comparative Example 1 had high transparency, but its solvent resistance was insufficient.
  • the films formed from the resin compositions prepared in Comparative Examples 2 to 4 had high solvent resistance and high transparency, but their reliability was insufficient.
  • the films formed from the resin compositions prepared in Comparative Examples 5 and 6 had high solvent resistance, high transparency and high reliability, but the residue level was higher than the standard or standard.
  • the film formed from the resin composition prepared in Comparative Example 7 had high solvent resistance and high transparency, but the residue level was equivalent to the standard.
  • the film formed from the resin composition prepared in Comparative Example 8 was highly soluble and highly transparent, but the residue level was higher than the standard.
  • the resin composition of the present invention is suitable as a material for forming a color filter lower layer film, a color filter upper layer film, a filler dispersion resist lower layer film, and the like in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays. is there. Further, when a color resist pattern is formed on the color filter lower layer film formed from the resin composition of the present invention, the generation of color resist residue can be suppressed, and the quality and yield of the device provided with the color filter can be improved. It is useful for.

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Abstract

[Problem] To provide a resin composition for forming a cured film that forms a lower layer and an upper layer of a color filter. [Solution] A resin composition which contains a homopolymer that has a structural unit represented by formula (1), a crosslinkable compound that has at least two alkoxyalkyl groups in each molecule, a photoacid generator, a surfactant and an organic solvent, wherein: the content of the crosslinkable compound is from 40% by mass to 60% by mass relative to the content of the homopolymer; and the content of the photoacid generator is at least 0.8% by mass relative to the total content of the homopolymer and the crosslinkable compound. (In the formula, R1 represents an alkyl group having 1-6 carbon atoms, which comprises at least one hydroxy group as a substituent.)

Description

低温硬化性樹脂組成物Low temperature curable resin composition
本発明は、イメージセンサ、ディスプレイデバイス等のカラーフィルターを備えたデバイスにおいて、該カラーフィルターの下層及び上層に形成される硬化膜を形成するために用いられる樹脂組成物に関する。特に、１１０℃を超えないベーク温度で硬化膜を形成可能な低温硬化性樹脂組成物に関する。 The present invention relates to a resin composition used for forming a cured film formed on a lower layer and an upper layer of a color filter in a device provided with a color filter such as an image sensor and a display device. In particular, the present invention relates to a low temperature curable resin composition capable of forming a cured film at a baking temperature not exceeding 110 ° C.
近年、ＣＣＤイメージセンサ、ＣＭＯＳイメージセンサ、液晶ディスプレイ、有機ＥＬディスプレイ等のデバイスは、カラーフィルターが欠かせない構成部品の一つになっている。 In recent years, devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays have become one of the indispensable components of color filters.
一般に、カラーフィルターの保護及びカラーフィルター表面の凹凸を平滑化することを目的として、カラーフィルター上層には保護膜、平坦化膜といった透明樹脂膜が形成される。また、カラーフィルターと下地基板との密着性を向上させること、及び回路配線部、遮光膜、インナーレンズ等の存在に起因する凹凸を平滑化することを目的として、カラーフィルター下層にも透明樹脂膜が形成される。このような透明樹脂膜を形成するための組成物は、例えば特許文献１乃至特許文献４に開示されている。 Generally, a transparent resin film such as a protective film or a flattening film is formed on the upper layer of the color filter for the purpose of protecting the color filter and smoothing the unevenness of the surface of the color filter. In addition, a transparent resin film is also applied to the lower layer of the color filter for the purpose of improving the adhesion between the color filter and the base substrate and smoothing the unevenness caused by the presence of the circuit wiring part, the light-shielding film, the inner lens, etc. Is formed. Compositions for forming such a transparent resin film are disclosed in, for example, Patent Documents 1 to 4.
カラーフィルターの形成には、例えば、顔料又は染料を含有する、赤、緑及び青の３色のカラーレジストが一般的に用いられる。３色のカラーレジストを用いたカラーフィルターの形成方法は、まず第１色目のカラーレジストを塗布し、露光、現像、及び加熱処理を行い、第１色目のカラーレジストパターンを形成する。その後、第１色目のカラーレジストパターンと同様にして、第２色目及び第３色目のカラーレジストパターンを形成し、カラーフィルターを形成する。 For the formation of the color filter, for example, a color resist of three colors of red, green and blue containing a pigment or a dye is generally used. In the method of forming a color filter using a three-color color resist, first, a color resist of the first color is applied, and exposure, development, and heat treatment are performed to form a color resist pattern of the first color. After that, the color resist patterns of the second color and the third color are formed in the same manner as the color resist pattern of the first color, and the color filter is formed.
このようなカラーフィルター形成方法において、カラーフィルターの色再現性の劣化及びカラーフィルターを備えたデバイスの歩留まり低下を抑制するために、カラーレジストパターン形成時にカラーレジストの残渣の発生を抑えることが重要となる。 In such a color filter forming method, it is important to suppress the generation of color resist residue when forming a color resist pattern in order to suppress the deterioration of the color reproducibility of the color filter and the decrease in the yield of the device equipped with the color filter. Become.
前記有機ＥＬディスプレイデバイスは、他のデバイスと比較して低温でのプロセスによって製造されることが望ましい。例えば、特許文献５に開示されているように、有機ＥＬ素子の特性維持の為、１１０℃よりも高い温度を掛けないことが要求される。したがって、前記カラーフィルターの上下層に形成する前記透明樹脂膜は、１１０℃以下の温度で樹脂組成物を硬化して形成できることが必要である。 It is desirable that the organic EL display device be manufactured by a process at a lower temperature than other devices. For example, as disclosed in Patent Document 5, in order to maintain the characteristics of the organic EL element, it is required not to apply a temperature higher than 110 ° C. Therefore, it is necessary that the transparent resin film formed on the upper and lower layers of the color filter can be formed by curing the resin composition at a temperature of 110 ° C. or lower.
特開２０００－３４４８６６号公報Japanese Unexamined Patent Publication No. 2000-344866 特開２００８－０３１３７０号公報Japanese Unexamined Patent Publication No. 2008-031370 特許第４２２２４５７号Patent No. 4222457 国際公開第２０１３／００５６１９号International Publication No. 2013/005619 国際公開第２０１７／２０３８８５号International Publication No. 2017/203885
前記透明樹脂膜上にカラーフィルターを形成する場合、前記のようなカラーレジストの残渣の発生を抑える特性が前記透明樹脂膜に要求される。しかしながら、従来の低温硬化性材料から形成される透明樹脂膜では、カラーレジストの残渣発生の十分な抑制効果と、永久膜としての十分な信頼性とを併せ持たないという問題があった。 When a color filter is formed on the transparent resin film, the transparent resin film is required to have the characteristics of suppressing the generation of color resist residues as described above. However, the transparent resin film formed from the conventional low-temperature curable material has a problem that it does not have a sufficient effect of suppressing the generation of residue of the color resist and a sufficient reliability as a permanent film.
本発明は、前記の事情に基づいてなされたものであり、その目的は、１１０℃を超えない、好ましくは１００℃以下の温度で、優れた耐溶剤性及び信頼性を有する硬化膜を形成でき、該硬化膜上にカラーフィルターを形成する際にカラーレジストの残渣の発生を抑えることができると共に、該カラーフィルター上に該硬化膜を形成できる、樹脂組成物を提供することである。また、本発明の他の目的は、優れた耐溶剤性及び信頼性を有するカラーフィルター下層膜及び／又はカラーフィルター上層膜を有する、カラーフィルターを備えたデバイスの作製方法を提供することである。 The present invention has been made based on the above circumstances, and an object thereof is to be able to form a cured film having excellent solvent resistance and reliability at a temperature not exceeding 110 ° C., preferably 100 ° C. or lower. It is an object of the present invention to provide a resin composition capable of suppressing the generation of color resist residue when forming a color filter on the cured film and forming the cured film on the color filter. Another object of the present invention is to provide a method for manufacturing a device having a color filter, which has a color filter lower layer film and / or a color filter upper layer film having excellent solvent resistance and reliability.
本発明者らは、前記の課題を解決するべく鋭意検討を行った結果、本発明を完成するに至った。すなわち本発明は、下記式（１）で表される構造単位を有するホモポリマー、アルコキシアルキル基を１分子中に少なくとも２個有する架橋性化合物、光酸発生剤、界面活性剤、及び有機溶剤を含有し、前記架橋性化合物の含有量は前記ホモポリマーの含有量に対し４０質量％乃至６０質量％であり、前記光酸発生剤の含有量は前記ホモポリマー及び前記架橋性化合物の含有量の和に対し少なくとも０．８質量％である、樹脂組成物である。
Figure JPOXMLDOC01-appb-C000002
 （前記式中、Ｒ１は置換基としてヒドロキシ基を少なくとも１つ有する炭素原子数１乃至６のアルキル基を表す。） As a result of diligent studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention uses homopolymers having a structural unit represented by the following formula (1), crosslinkable compounds having at least two alkoxyalkyl groups in one molecule, photoacid generators, surfactants, and organic solvents. The content of the crosslinkable compound is 40% by mass to 60% by mass with respect to the content of the homopolymer, and the content of the photoacid generator is the content of the homopolymer and the crosslinkable compound. The resin composition is at least 0.8% by mass based on the sum.
Figure JPOXMLDOC01-appb-C000002
 (In the above formula, R 1 represents an alkyl group having at least one hydroxy group as a substituent and having 1 to 6 carbon atoms.)
前記光酸発生剤から発生する酸は例えば超酸であり、その酸解離定数ｐＫａは例えば－７より小さい。 The acid generated from the photoacid generator is, for example, a superacid, and its acid dissociation constant pKa is, for example, smaller than -7.
前記光酸発生剤から発生する酸は、例えばブレンステッド酸である。 The acid generated from the photoacid generator is, for example, Bronsted acid.
前記光酸発生剤は、例えばＮ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド又はその誘導体、又はジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物である。 The photoacid generator is, for example, N- (trifluoromethanesulfonyloxy) -1,8-naphthalimide or a derivative thereof, or a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound.
本発明の他の態様は、基材上に本発明の樹脂組成物を塗布する工程、該樹脂組成物を７５℃乃至１１０℃でプリベークし、近紫外線で露光後、７５℃乃至１１０℃でポストベークしてカラーフィルター下層膜を形成する工程、及び前記カラーフィルター下層膜上にカラーレジストを用いてカラーフィルターを形成する工程を有する、カラーフィルターを備えたデバイスの作製方法である。 Another aspect of the present invention is a step of applying the resin composition of the present invention on a substrate, the resin composition is prebaked at 75 ° C. to 110 ° C., exposed to near ultraviolet rays, and then posted at 75 ° C. to 110 ° C. A method for manufacturing a device including a color filter, which comprises a step of baking to form a color filter lower layer film and a step of forming a color filter on the color filter lower layer film using a color resist.
前記カラーフィルターを備えたデバイスの作製方法は、前記カラーフィルター上に前記樹脂組成物を塗布する工程、及び該樹脂組成物を７５℃乃至１１０℃でプリベークし、近紫外線で露光後、７５℃乃至１１０℃でポストベークしてカラーフィルター上層膜を形成する工程をさらに有してもよい。 The method for producing a device provided with the color filter includes a step of applying the resin composition on the color filter, a prebaking of the resin composition at 75 ° C to 110 ° C, exposure to near ultraviolet rays, and then 75 ° C to It may further have a step of post-baking at 110 ° C. to form a color filter upper layer film.
前記プリベーク及びポストベークは、１００℃以下で行うことが好ましい。 The pre-baking and post-baking are preferably performed at 100 ° C. or lower.
本発明の樹脂組成物から形成されるカラーフィルター下層膜又はカラーフィルター上層膜は、優れた耐薬品性、耐熱性及び透明性を有する。これにより、本発明の樹脂組成物から形成されるカラーフィルター下層膜又はカラーフィルター上層膜は、その形成工程、又は配線等の周辺装置の形成工程において、酸もしくはアルカリ溶液等の薬液、又は溶剤に曝される処理や、スパッタリング、及びドライエッチングに曝される処理が行われる場合に、素子が劣化もしくは損傷する可能性を著しく減少できる。また、本発明の樹脂組成物からカラーフィルター下層膜を形成し、その上にカラーレジストを塗布する場合には、該カラーレジストとのミキシングの問題、該カラーレジストの残渣発生の問題、及び上記薬液によるカラーフィルター下層膜の変形及び剥離といった問題も著しく減少できる。さらに、本発明の樹脂組成物から形成されるカラーフィルター下層膜又はカラーフィルター上層膜は、露光後、アルカリ性現像液を用いて現像することによって、所望のパターンを形成することができる。したがって、本発明の樹脂組成物は、カラーフィルター下層膜又はカラーフィルター上層膜を形成する材料として好適である。 The color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention has excellent chemical resistance, heat resistance and transparency. As a result, the color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention can be used as a chemical solution such as an acid or alkaline solution or a solvent in the forming step thereof or the forming step of peripheral devices such as wiring. The possibility of deterioration or damage of the element can be significantly reduced when the treatment is exposed, sputtering, and dry etching is performed. Further, when a color filter lower layer film is formed from the resin composition of the present invention and a color resist is applied thereto, the problem of mixing with the color resist, the problem of generation of residue of the color resist, and the above-mentioned chemical solution Problems such as deformation and peeling of the underlayer film of the color filter due to the above can be significantly reduced. Further, the color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention can form a desired pattern by developing with an alkaline developer after exposure. Therefore, the resin composition of the present invention is suitable as a material for forming a color filter lower layer film or a color filter upper layer film.
本発明は、特定のホモポリマー、アルコキシアルキル基を１分子中に少なくとも２個有する架橋性化合物、光酸発生剤、界面活性剤及び有機溶剤を含有する樹脂組成物である。以下、各成分の詳細を説明する。本発明の樹脂組成物から有機溶剤を除いた固形分は通常、０．０１質量％乃至５０質量％である。 The present invention is a resin composition containing a specific homopolymer, a crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant and an organic solvent. The details of each component will be described below. The solid content of the resin composition of the present invention excluding the organic solvent is usually 0.01% by mass to 50% by mass.
＜ホモポリマー＞
本発明の樹脂組成物に含まれるホモポリマーは、前記式（１）で表される構造単位を有するポリマーである。前記式（１）において、Ｒ１で表される基としては、例えば、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ジヒドロキシプロピル基、及びジヒドロキシブチル基が挙げられる。 <Homopolymer>
The homopolymer contained in the resin composition of the present invention is a polymer having a structural unit represented by the above formula (1). In the above formula (1), examples of the group represented by R 1 include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a dihydroxypropyl group, and a dihydroxybutyl group.
前記式（１）で表される構造単位を形成する化合物（モノマー）としては、例えば、ヒドロキシメチルメタクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレート、４－ヒドロキシブチルメタクリレート、３，４－ジヒドロキシブチルメタクリレート、ジエチレングリコールモノメタクリレート、及びジプロピレングリコールモノメタクリレートが挙げられる。本発明の樹脂組成物に該式（１）で表される構造単位を有するホモポリマーを用いることによって、該樹脂組成物から形成されるカラーフィルター下層膜上にカラーフィルターを形成後、該カラーフィルター下層膜上に発生するカラーレジストの残渣を抑制できる。 Examples of the compound (monomer) forming the structural unit represented by the formula (1) include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydrokipropyl methacrylate, 3-hydroxypropyl methacrylate, and 2,3-dihydroxy. Examples thereof include propyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3,4-dihydroxybutyl methacrylate, diethylene glycol monomethacrylate, and dipropylene glycol monomethacrylate. By using a homopolymer having a structural unit represented by the formula (1) in the resin composition of the present invention, a color filter is formed on a color filter lower layer film formed from the resin composition, and then the color filter is formed. The residue of the color resin generated on the lower layer film can be suppressed.
前記ホモポリマーの重量平均分子量は通常、１，０００乃至２００，０００であり、好ましくは３，０００乃至１００，０００である。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により得られる値である。 The weight average molecular weight of the homopolymer is usually 1,000 to 200,000, preferably 3,000 to 100,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC).
また、本発明の樹脂組成物における前記ホモポリマーの含有量は、該樹脂組成物の固形分中の含有量に基づいて通常、３０質量％乃至９９質量％であり、好ましくは６０質量％乃至７５質量％である。 The content of the homopolymer in the resin composition of the present invention is usually 30% by mass to 99% by mass, preferably 60% by mass to 75% based on the content in the solid content of the resin composition. It is mass%.
本発明において、前記ホモポリマーを得る方法は特に限定されないが、一般的には、前記式（１）で表される構造単位を形成する化合物（モノマー）を、重合開始剤存在下の溶剤中において、通常５０℃乃至１２０℃の温度下で重合反応させることにより得られる。このようにして得られるホモポリマーは、通常、溶剤に溶解した溶液状態であり、この状態で単離することなく、本発明の樹脂組成物に用いることもできる。 In the present invention, the method for obtaining the homopolymer is not particularly limited, but in general, the compound (monomer) forming the structural unit represented by the formula (1) is placed in a solvent in the presence of a polymerization initiator. , Usually obtained by polymerizing at a temperature of 50 ° C to 120 ° C. The homopolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the resin composition of the present invention without being isolated in this state.
また、上記のようにして得られたホモポリマーの溶液を、攪拌させたヘキサン、ジエチルエーテル、トルエン、メタノール、水等の貧溶媒に投入して該ホモポリマーを再沈殿させ、生成した沈殿物をデカンテーション又はろ過し、必要に応じて洗浄後、常圧又は減圧下で常温乾燥又は加熱乾燥することで、該ホモポリマーをオイル状物又は粉体とすることができる。このような操作により、前記ホモポリマーと共存する重合開始剤や未反応化合物を除去することができる。本発明においては、該ホモポリマーのオイル状物又は粉体をそのまま用いてもよく、あるいはそのオイル状物又は粉体を、例えば後述する有機溶剤に再溶解して溶液の状態として用いてもよい。 Further, the homopolymer solution obtained as described above was put into a stirred poor solvent such as hexane, diethyl ether, toluene, methanol and water to reprecipitate the homopolymer, and the resulting precipitate was produced. The homopolymer can be made into an oil or powder by decanting or filtering, washing if necessary, and then drying at room temperature or heating under normal pressure or reduced pressure. By such an operation, the polymerization initiator and the unreacted compound coexisting with the homopolymer can be removed. In the present invention, the oily substance or powder of the homopolymer may be used as it is, or the oily substance or powder thereof may be redissolved in, for example, an organic solvent described later and used as a solution. ..
＜架橋性化合物＞
本発明の樹脂組成物に含まれる架橋性化合物は、アルコキシアルキル基を１分子中に少なくとも２個有する。該架橋性化合物として、例えば、アルコキシアルキル化された窒素原子を有する化合物を挙げることができる。 <Crosslinkable compound>
The crosslinkable compound contained in the resin composition of the present invention has at least two alkoxyalkyl groups in one molecule. Examples of the crosslinkable compound include compounds having an alkoxyalkylated nitrogen atom.
前記アルコキシアルキル化された窒素原子を有する化合物としては、例えば、（ポリ）メチロール化メラミン、（ポリ）メチロール化グリコールウリル、（ポリ）メチロール化ベンゾグアナミン、（ポリ）メチロール化ウレア等の、一分子内に複数個の活性メチロール基を有する含窒素化合物であって、そのメチロール基中のヒドロキシ基の水素原子の少なくとも一つが、メチル基、ブチル基等のアルキル基によって置換された化合物を挙げることができる。 Examples of the compound having an alkoxyalkylated nitrogen atom include (poly) methylolated melamine, (poly) methylolated glycoluryl, (poly) methylolated benzoguanamine, and (poly) methylolated urea in one molecule. Examples of a nitrogen-containing compound having a plurality of active methylol groups in which at least one hydrogen atom of the hydroxy group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group can be mentioned. ..
前記アルコキシアルキル化された窒素原子を有する化合物は、複数の置換化合物を混合した混合物である場合があり、一部自己縮合してなるオリゴマー成分を含む混合物も存在し、そのような混合物も使用することができる。より具体的には、例えば、ヘキサメトキシメチルメラミン（日本サイテックインダストリーズ（株）製、ＣＹＭＥＬ〔登録商標〕３０３）、テトラブトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、ＣＹＭＥＬ〔登録商標〕１１７０）、テトラメトキシメチルベンゾグアナミン（日本サイテックインダストリーズ（株）製、ＣＹＭＥＬ〔登録商標〕１１２３）等のＣＹＭＥＬシリーズの商品、テトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）等のＰＯＷＤＥＲＬＩＮＫシリーズの商品、及びメチル化メラミン樹脂（（株）三和ケミカル製、ニカラック〔登録商標〕ＭＷ－３０ＨＭ、同ＭＷ－３９０、同ＭＷ－１００ＬＭ、同ＭＸ－７５０ＬＭ）、メチル化尿素樹脂（（株）三和ケミカル製、ニカラック〔登録商標〕ＭＸ－２７０、同ＭＸ－２８０、同ＭＸ－２９０）等のニカラックシリーズの商品、を挙げることができる。これらの架橋性化合物は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 The compound having an alkoxyalkylated nitrogen atom may be a mixture of a plurality of substituted compounds, and there is also a mixture containing an oligomer component which is partially self-condensed, and such a mixture is also used. be able to. More specifically, for example, hexamethoxymethylmelamine (manufactured by Nippon Cytec Industries Co., Ltd., CYMEL [registered trademark] 303), tetrabutoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd., CYMEL [registered trademark] 1170). , Tetramethoxymethylbenzoguanamine (manufactured by Nippon Cytec Industries Co., Ltd., CYMEL [registered trademark] 1123) and other CYMEL series products, tetramethoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd., POWDERLINK [registered trademark] 1174), etc. POWDERLINK series products, methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., Nicarac [registered trademark] MW-30HM, MW-390, MW-100LM, MX-750LM), methylated urea resin ( Examples of Nikalac series products such as Nikalac (registered trademark) MX-270, MX-280, and MX-290) manufactured by Sanwa Chemical Co., Ltd. These crosslinkable compounds may be used alone or in combination of two or more.
本発明の樹脂組成物における架橋性化合物の含有量は、該樹脂組成物中の前記ホモポリマーの含有量に基づいて、好ましくは４０質量％乃至６０質量％である。本発明の樹脂組成物において前記架橋性化合物の含有量が過剰又は過少な場合、該樹脂組成物から形成されるカラーフィルター下層膜上にカラーフィルターを形成後、該カラーフィルター下層膜上に観察されるカラーレジストの残渣が多くなる虞がある。 The content of the crosslinkable compound in the resin composition of the present invention is preferably 40% by mass to 60% by mass based on the content of the homopolymer in the resin composition. When the content of the crosslinkable compound in the resin composition of the present invention is excessive or too small, it is observed on the color filter lower layer film after forming the color filter on the color filter lower layer film formed from the resin composition. There is a risk that the color resist residue will increase.
＜光酸発生剤＞
本発明の樹脂組成物に含まれる光酸発生剤は、露光により強酸、好ましくは酸解離定数ｐＫａが－７より小さい超酸が発生する化合物である。該化合物の具体例として、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物が挙げられる。 <Photoacid generator>
The photoacid generator contained in the resin composition of the present invention is a compound that generates a strong acid, preferably a superacid having an acid dissociation constant pKa of less than −7, upon exposure. Specific examples of the compound include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.
前記オニウム塩化合物の具体例として、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ－ｎ－ブタンスルホネート、ジフェニルヨードニウムパーフルオロ－ｎ－オクタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムカンファースルホネート、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート等のヨードニウム塩化合物、及びトリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムノナフルオロ－ｎ－ブタンスルホネート、トリフェニルスルホニウムカンファースルホネート、トリフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムヘキサフルオロホスフェート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムヘキサフルオロアンチモネート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等のスルホニウム塩化合物が挙げられる。該オニウム塩化合物の中で、スルホニウム塩化合物が好ましく、ｉ線（３６５ｎｍ）を用いた露光により酸が発生する化合物としてはジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物がより好ましい。 Specific examples of the onium salt compound include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butane sulfonate, diphenyliodonium perfluoro-n-octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-). Iodonium salt compounds such as tert-butylphenyl) iodonium camphor sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, tri Phenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl ] Sulfonium hexafluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] Examples thereof include sulfonium salt compounds such as sulfonium tetrakis (pentafluorophenyl) borate. Among the onium salt compounds, a sulfonium salt compound is preferable, and a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound is more preferable as a compound in which an acid is generated by exposure using i-ray (365 nm).
前記スルホンイミド化合物の具体例として、Ｎ－（トリフルオロメタンスルホニルオキシ）スクシンイミド、Ｎ－（ノナフルオロ－ｎ－ブタンスルホニルオキシ）スクシンイミド、Ｎ－（カンファースルホニルオキシ）スクシンイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－２－アルキル－１，８－ナフタルイミド、Ｎ－（トリフルオロメタンスルホニルオキシ）－３－アルキル－１，８－ナフタルイミド及びＮ－（トリフルオロメタンスルホニルオキシ）－４－アルキル－１，８－ナフタルイミドが挙げられる。該スルホンイミド化合物の中で、Ｎ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド、及びその誘導体が好ましい。 Specific examples of the sulfonylimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy)- 1,8-Naphthalimide, N- (trifluoromethanesulfonyloxy) -2-alkyl-1,8-naphthalimide, N- (trifluoromethanesulfonyloxy) -3-alkyl-1,8-naphthalimide and N- ( Examples thereof include trifluoromethanesulfonyloxy) -4-alkyl-1,8-naphthalimide. Among the sulfonimide compounds, N- (trifluoromethanesulfonyloxy) -1,8-naphthalimide and its derivatives are preferable.
前記ジスルホニルジアゾメタン化合物の具体例として、ビス（トリフルオロメチルスルホニル）ジアゾメタンが挙げられる。 Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane.
前記光酸発生剤の具体例として、アデカアークルズ（登録商標）ＳＰ－０５６、同ＳＰ－０６６、同ＳＰ－１４０、同ＳＰ－１４１、同ＳＰ－０８２、同ＳＰ－６０１、同ＳＰ－６０６、同ＳＰ－７０１、同ＳＰ－１５０、同ＳＰ－１７０、同ＳＰ－１７１（以上、（株）ＡＤＥＫＡ製）、ＣＰＩ（登録商標）－１１０Ｐ、同－１１０Ｂ、同－３１０Ｂ、同－２１０Ｓ、同－１００Ｐ、同－１０１Ａ、同－２００Ｋ（以上、サンアプロ（株）製）、ＤＰＩ－１０５、ＤＰＩ－１０６、ＤＰＩ－１０９、ＤＰＩ－２０１、ＢＩ－１０５、ＭＰＩ－１０５、ＭＰＩ－１０６、ＭＰＩ－１０９、ＢＢＩ－１０２、ＢＢＩ－１０３、ＢＢＩ－１０５、ＢＢＩ－１０６、ＢＢＩ－１０９、ＢＢＩ－１１０、ＢＢＩ－２００、ＢＢＩ－２０１、ＢＢＩ－３００、ＢＢＩ－３０１、ＴＰＳ－１０２、ＴＰＳ－１０３、ＴＰＳ－１０５、ＴＰＳ－１０６、ＴＰＳ－１０９、ＴＰＳ－２００、ＴＰＳ－３００、ＴＰＳ－１０００、ＨＤＳ－１０９、ＭＤＳ－１０３、ＭＤＳ－１０５、ＭＤＳ－２０５、ＭＤＳ－２０９、ＢＤＳ－１０９、ＭＮＰＳ－１０９、ＤＴＳ－１０２、ＤＴＳ－１０３、ＤＴＳ－１０５、ＤＴＳ－２００、ＮＤＳ－１０３、ＮＤＳ－１０５、ＮＤＳ－１５５、ＮＤＳ－１６５、ＳＩ－１０５、ＮＤＩ－１０５、ＮＤＩ－１０９、ＮＡＩ－１０５、ＮＡＩ－１０９（以上、みどり化学（株）製）が挙げられる。これらの光酸発生剤は、１種単独で又は２種以上を組み合わせて用いることができる。 As specific examples of the photoacid generator, ADEKA Arklus (registered trademark) SP-056, SP-066, SP-140, SP-141, SP-082, SP-601, SP-606. , SP-701, SP-150, SP-170, SP-171 (all manufactured by ADEKA Corporation), CPI (registered trademark) -110P, -110B, -310B, -210S, Same as -100P, Same as -101A, Same as -200K (all manufactured by Sun Apro Co., Ltd.), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI -109, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301, TPS-102, TPS-103 , TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-205, MDS-209, BDS-109, MNPS -109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS-165, SI-105, NDI-105, NDI-109, NAI-105 , NAI-109 (above, manufactured by Midori Kagaku Co., Ltd.). These photoacid generators can be used alone or in combination of two or more.
また、本発明の樹脂組成物における前記光酸発生剤の含有量は、該樹脂組成物中の前記ホモポリマー及び前記架橋性化合物の含有量の和に基づいて通常、０．８質量％乃至２０質量％であり、好ましくは１．０質量％乃至１５質量％である。本発明の樹脂組成物において前記光酸発生剤の含有量が過少な場合、該樹脂組成物から形成される膜の耐溶剤性又は信頼性が不十分となる虞がある。 The content of the photoacid generator in the resin composition of the present invention is usually 0.8% by mass to 20% based on the sum of the contents of the homopolymer and the crosslinkable compound in the resin composition. It is by mass, preferably 1.0% by mass to 15% by mass. If the content of the photoacid generator is too small in the resin composition of the present invention, the solvent resistance or reliability of the film formed from the resin composition may be insufficient.
＜界面活性剤＞
本発明の樹脂組成物は、塗布性を向上させる目的で、界面活性剤を含有する。該界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（以上、三菱マテリアル電子化成（株）製）、メガファック〔登録商標〕Ｆ－１７１、同Ｆ－１７３、同Ｒ－３０、同Ｒ－４０、同Ｒ－４０－ＬＭ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（以上、住友スリーエム（株）製）、アサヒガード〔登録商標〕ＡＧ７１０、サーフロン〔登録商標〕Ｓ－３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（ＡＧＣ（株）製）、ＦＴＸ－２０６Ｄ、ＦＴＸ－２１２Ｄ、ＦＴＸ－２１８、ＦＴＸ－２２０Ｄ、ＦＴＸ－２３０Ｄ、ＦＴＸ－２４０Ｄ、ＦＴＸ－２１２Ｐ、ＦＴＸ－２２０Ｐ、ＦＴＸ－２２８Ｐ、ＦＴＸ－２４０Ｇ、ＤＦＸ－１８等のフタージェントシリーズ（（株）ネオス製）等のフッ素系界面活性剤、及びオルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）を挙げることができる。これらの界面活性剤は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 <Surfactant>
The resin composition of the present invention contains a surfactant for the purpose of improving coatability. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Polysorbate fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, Ftop [registered trademark] EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck [registered trademark] F-171 , F-173, R-30, R-40, R-40-LM (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431 (above, manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [Registered Trademarks] AG710, Surflon [Registered Trademarks] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), FTX-206D, FTX-212D, FTX- 218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18, etc. Examples thereof include an activator and an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). These surfactants may be used alone or in combination of two or more.
本発明の樹脂組成物における界面活性剤の含有量は、該樹脂組成物中の前記ホモポリマーの含有量に基づいて、通常０．００１質量％乃至３質量％であり、好ましくは０．０１質量％乃至２質量％であり、より好ましくは０．１質量％乃至１質量％である。 The content of the surfactant in the resin composition of the present invention is usually 0.001% by mass to 3% by mass, preferably 0.01% by mass, based on the content of the homopolymer in the resin composition. % To 2% by mass, more preferably 0.1% by mass to 1% by mass.
＜有機溶剤＞
本発明の樹脂組成物に含まれる有機溶剤としては、該樹脂組成物に含まれる固形分を溶解するものであれば特に限定されない。そのような有機溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチ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、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、２－ヘプタノン、γ－ブチロラクトン、Ｎ－メチルピロリドン、及びＮ－エチルピロリドンを挙げることができる。これらの有機溶剤は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 <Organic solvent>
The organic solvent contained in the resin composition of the present invention is not particularly limited as long as it dissolves the solid content contained in the resin composition. Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate. , 2-Hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, N-methylpyrrolidone, and N-ethylpyrrolidone. These organic solvents may be used alone or in combination of two or more.
前記有機溶剤の中でも、本発明の樹脂組成物を基材上に塗布して形成される塗膜のレベリング性の向上の観点から、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、２－ヘプタノン、乳酸エチル、乳酸ブチル、シクロペンタノン、シクロヘキサノン及びγ－ブチロラクトンが好ましい。 Among the above organic solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether, from the viewpoint of improving the leveling property of the coating film formed by applying the resin composition of the present invention on the substrate. , Propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, cyclopentanone, cyclohexanone and γ-butyrolactone are preferred.
＜その他添加剤＞
本発明の樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、光安定剤、紫外線吸収剤、増感剤、可塑剤、酸化防止剤、密着助剤、消泡剤等の添加剤を含むことができる。 <Other additives>
The resin composition of the present invention may be a light stabilizer, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, an antifoaming agent, etc., as required, as long as the effects of the present invention are not impaired. Additives can be included.
＜樹脂組成物の調製方法＞
本発明の樹脂組成物の調製方法は、特に限定されないが、例えば、前記式（１）で表される構造単位を有するホモポリマーの溶液、架橋性化合物、光酸発生剤及び界面活性剤を所定の割合で有機溶剤に溶解し、均一な溶液とする方法が挙げられる。さらに、この調製方法の適当な段階において、必要に応じて、その他の添加剤を更に添加して混合する方法が挙げられる。 <Preparation method of resin composition>
The method for preparing the resin composition of the present invention is not particularly limited, and for example, a solution of a homopolymer having a structural unit represented by the above formula (1), a crosslinkable compound, a photoacid generator and a surfactant are specified. A method of dissolving in an organic solvent at the ratio of 1 to obtain a uniform solution can be mentioned. Further, at an appropriate stage of this preparation method, a method of further adding and mixing other additives, if necessary, can be mentioned.
＜カラーフィルター下層膜又はカラーフィルター上層膜の作製方法＞
本発明の樹脂組成物を用いたカラーフィルター下層膜又はカラーフィルター上層膜の作製方法について説明する。基材（例えば、半導体基板、ガラス基板、石英基板、シリコンウエハー、及びこれらの表面に各種金属膜、平坦化膜、カラーフィルター、有機ＥＬ素子等が形成された基板）上に、スピナー、コーター等の適当な塗布方法により本発明の樹脂組成物を塗布し、その後、ホットプレート、オーブン等の加熱手段を用いてプリベークすることにより、塗膜が形成される。続いて露光機を用いて塗膜を露光する。さらにホットプレート、オーブン等の加熱手段を用いてポストベークして硬化させて、カラーフィルター下層膜又はカラーフィルター上層膜を作製する。前記樹脂組成物を塗布後又はプリベーク後に現像処理を含んでもよい。前記プリベーク及びポストベーク条件は、ベーク温度７５℃乃至１１０℃、ベーク時間０．３分乃至６０分間の中から適宜選択される。該ポストベークは２ステップ以上処理してもよい。前記露光には、例えば、近紫外線（例えばｉ線）を使用することができる。また、本発明の樹脂組成物から形成されるカラーフィルター下層膜の膜厚は例えば０．０６μｍ乃至０．５μｍであり、本発明の樹脂組成物から形成されるカラーフィルター上層膜の膜厚は例えば０．３μｍ乃至１．０μｍである。 <Method of producing color filter lower layer film or color filter upper layer film>
A method for producing a color filter lower layer film or a color filter upper layer film using the resin composition of the present invention will be described. Spinners, coaters, etc. on a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films, flattening films, color filters, organic EL elements, etc. are formed). A coating film is formed by applying the resin composition of the present invention by an appropriate coating method of the above, and then prebaking using a heating means such as a hot plate or an oven. Subsequently, the coating film is exposed using an exposure machine. Further, it is post-baked and cured using a heating means such as a hot plate or an oven to prepare a color filter lower layer film or a color filter upper layer film. The development treatment may be included after the resin composition is applied or prebaked. The pre-baking and post-baking conditions are appropriately selected from a baking temperature of 75 ° C. to 110 ° C. and a baking time of 0.3 minutes to 60 minutes. The post-bake may be processed in two or more steps. For the exposure, for example, near ultraviolet rays (for example, i-rays) can be used. The thickness of the color filter lower layer film formed from the resin composition of the present invention is, for example, 0.06 μm to 0.5 μm, and the thickness of the color filter upper layer film formed from the resin composition of the present invention is, for example. It is 0.3 μm to 1.0 μm.
以下に実施例及び比較例に基づいて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものでない。 The present invention will be described in more detail below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
〔下記合成例で得られたホモポリマーの重量平均分子量の測定〕
ホモポリマーの分子量はＧＰＣ装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として重量平均分子量（Ｍｗ）を算出した。
ＧＰＣ装置：昭和電工（株）製ＧＰＣシステム（Ｓｈｏｄｅｘ〔登録商標〕ＧＰＣ－１０１）
カラム：Ｓｈｏｄｅｘ〔登録商標〕ＫＤ－８００ＲＨ、ＫＤ－８００ＲＬ、ＫＤ－８０３及びＫＤ－８０５
カラム温度：５０℃
溶離液：Ｎ，Ｎ－ジメチルホルムアミド［添加剤として、臭化リチウム－水和物（ＬｉＢｒ・Ｈ２Ｏ）３０ｍｍｏｌ／Ｌ、リン酸・無水結晶（ｏ－リン酸）３０ｍｍｏｌ／Ｌ、及びテトラヒドロフラン（ＴＨＦ）１０ｍｌ／Ｌを含む。］
流速：１．０ｍＬ／分
検量線作成用標準サンプル：東ソー（株）製　ＴＳＫ　標準ポリエチレンオキサイド［重量平均分子量（Ｍｗ）９００，０００、１５０，０００、１００，０００、３０，０００］、及びポリマーラボラトリー社製　ポリエチレングリコール［ピークトップ分子量（Ｍｐ）１２，０００、４，０００、１，０００］
ピークが重なるのを避けるため、Ｍｗが９００，０００、１００，０００である標準ポリエチレンオキサイド及びＭｐが１２，０００、１，０００であるポリエチレングリコールの４種を混合したサンプル、並びにＭｗが１５０，０００、３０，０００である標準ポリエチレンオキサイド及びＭｐが４，０００であるポリエチレングリコールの３種を混合したサンプル、すなわち２サンプルを別々に測定した。 [Measurement of weight average molecular weight of homopolymer obtained in the following synthetic example]
The molecular weight of the homopolymer was measured by a GPC apparatus, and the weight average molecular weight (Mw) was calculated as a polyethylene glycol or polyethylene oxide conversion value.
GPC device: GPC system manufactured by Showa Denko KK (Shodex [registered trademark] GPC-101)
Columns: Shodex® KD-800RH, KD-800RL, KD-803 and KD-805
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide [As additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) 30 mmol / L, and tetrahydrofuran ( THF) contains 10 ml / L. ]
Flow velocity: 1.0 mL / Standard sample for preparing a calibration curve: TSK standard polyethylene oxide manufactured by Toso Co., Ltd. [weight average molecular weight (Mw) 900,000, 150,000, 100,000, 30,000], and polymer laboratory Polyethylene glycol manufactured by [Peak Top Molecular Weight (Mp) 12,000, 4,000, 1,000]
In order to avoid overlapping peaks, a sample in which four types of standard polyethylene oxide having Mw of 900,000 and 100,000 and polyethylene glycol having Mp of 12,000 and 1,000 are mixed, and Mw of 150,000 Samples in which three types of standard polyethylene oxide having an Mp of 30,000 and polyethylene glycol having an Mp of 4,000 were mixed, that is, two samples were measured separately.
［ポリマーの合成］
＜合成例１＞
２－ヒドロキシエチルメタクリレート４０．０ｇ及び２，２’－アゾビスイソブチロニトリル３．０ｇを、プロピレングリコールモノメチルエーテル８０．０ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル４９．０ｇを７０℃に保持したフラスコ中に４時間かけて滴下した。滴下終了後、さらに１８時間反応させて、ホモポリマーの溶液（固形分濃度２５質量％）を得た。得られたホモポリマーの重量平均分子量Ｍｗは２４，２００であった。 [Polymer synthesis]
<Synthesis example 1>
After dissolving 40.0 g of 2-hydroxyethyl methacrylate and 3.0 g of 2,2'-azobisisobutyronitrile in 80.0 g of propylene glycol monomethyl ether, this solution was added to 49.0 g of propylene glycol monomethyl ether. It was added dropwise over 4 hours in a flask maintained at 70 ° C. After completion of the dropping, the reaction was further carried out for 18 hours to obtain a homopolymer solution (solid content concentration: 25% by mass). The weight average molecular weight Mw of the obtained homopolymer was 24,200.
＜合成例２＞　
２－ヒドロキシプロピルアクリレート３０．２ｇ、ベンジルアクリレート１０．０ｇ及び２，２’－アゾビスイソブチロニトリル３．４ｇをプロピレングリコールモノメチルエーテル８０．９ｇに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル４９．８ｇを７０℃に保持したフラスコ中に４時間かけて滴下した。滴下終了後、さらに１８時間反応させて、コポリマーの溶液（固形分濃度２５．０質量％）を得た。得られたコポリマーの重量平均分子量Ｍｗは１３，５００であった。 <Synthesis example 2>
After dissolving 30.2 g of 2-hydroxypropyl acrylate, 10.0 g of benzyl acrylate and 3.4 g of 2,2'-azobisisobutyronitrile in 80.9 g of propylene glycol monomethyl ether, this solution was mixed with propylene glycol monomethyl. 49.8 g of ether was added dropwise to the flask kept at 70 ° C. over 4 hours. After completion of the dropping, the reaction was further carried out for 18 hours to obtain a solution of the copolymer (solid content concentration 25.0% by mass). The weight average molecular weight Mw of the obtained copolymer was 13,500.
［樹脂組成物の調製］
＜実施例１＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０２８ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 [Preparation of resin composition]
<Example 1>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. SP-606 (manufactured by ADEKA Co., Ltd.) 0.028 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl ether 26. It was dissolved in 3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜実施例２＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、光酸発生剤としてＣＰＩ－２１０Ｓ（サンアプロ（株）製）０．１４ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Example 2>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. CPI-210S (manufactured by Sun Appro Co., Ltd.) 0.14 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl ether 26. It was dissolved in 3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜実施例３＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、光酸発生剤としてＣＰＩ－１１０Ｂ（サンアプロ（株）製）０．１４ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Example 3>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. CPI-110B (manufactured by Sun Appro Co., Ltd.) 0.14 g and Megafuck® R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl ether 26. It was dissolved in 3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜実施例４＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））１．２ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０３２ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１５．８ｇ及びプロピレングリコールモノメチルエーテル３０．９ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Example 4>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 1.2 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. SP-606 (manufactured by ADEKA Co., Ltd.) 0.032 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 15.8 g and propylene glycol monomethyl ether 30. It was dissolved in 9 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜比較例１＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、熱酸発生剤としてＴＡＧ２６８９（ＫＩＮＧ　ＩＮＤＵＳＴＲＩＥＳ社製）０．０２８ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Comparative example 1>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a thermoacid generator. 0.028 g of TAG2689 (manufactured by KING INDUSTRIES) and 0.002 g of Megafuck (registered trademark) R-40 (manufactured by DIC Co., Ltd.) are dissolved in 13.9 g of propylene glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. It was made into a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜比較例２＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、酸化合物としてｐ－トルエンスルホン酸（東京化成工業（株）製）０．０２８ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Comparative example 2>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, p- as an acid compound. 0.028 g of toluenesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.002 g of Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.), 13.9 g of propylene glycol monoethyl ether and propylene glycol monomethyl ether. It was dissolved in 26.3 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜比較例３＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、酸化合物としてピリジニウムｐ－トルエンスルホナート（東京化成工業（株）製）０．０２８ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Comparative example 3>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, and pyridinium p as an acid compound. -Toluene sulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.028 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 13.9 g and propylene glycol monomethyl It was dissolved in 26.3 g of ether to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜比較例４＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、酸化合物としてピリジニウムｐ－トルエンスルホナート（東京化成工業（株）製）０．１４ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１４．４ｇ及びプロピレングリコールモノメチルエーテル２７．６ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Comparative example 4>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, and pyridinium p as an acid compound. -Toluene sulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.14 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 14.4 g and propylene glycol monomethyl It was dissolved in 27.6 g of ether to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
＜比較例５＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．２ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０２２ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１０．９ｇ及びプロピレングリコールモノメチルエーテル１９．４ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。本比較例は、架橋性化合物の含有量が過少な例である。 <Comparative example 5>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.2 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. SP-606 (manufactured by ADEKA Co., Ltd.) 0.022 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 10.9 g and propylene glycol monomethyl ether 19. It was dissolved in 4 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinkable compound is too small.
＜比較例６＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））１．６ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０３６ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１７．８ｇ及びプロピレングリコールモノメチルエーテル３５．６ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。本比較例は、架橋性化合物の含有量が過剰な例である。 <Comparative Example 6>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 1.6 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. SP-606 (manufactured by ADEKA Co., Ltd.) 0.036 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 17.8 g and propylene glycol monomethyl ether 35. It was dissolved in 6 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinkable compound is excessive.
＜比較例７＞
合成例１で得られたホモポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．４ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０２４ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、プロピレングリコールモノエチルエーテル１１．９ｇ及びプロピレングリコールモノメチルエーテル２１．７ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。本比較例は、架橋性化合物の含有量が過少な例である。 <Comparative Example 7>
8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.4 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, as a photoacid generator. SP-606 (manufactured by ADEKA Co., Ltd.) 0.024 g and Megafuck [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002 g, propylene glycol monoethyl ether 11.9 g and propylene glycol monomethyl ether 21. It was dissolved in 7 g to prepare a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinkable compound is too small.
＜比較例８＞
合成例２で得られたコポリマーの溶液８．０ｇ、架橋性化合物としてテトラメトキシメチルグリコールウリル（ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４（日本サイテックインダストリーズ（株）製））０．８ｇ、光酸発生剤としてＳＰ－６０６（（株）ＡＤＥＫＡ製）０．０２８ｇ及びメガファック〔登録商標〕Ｒ－４０（ＤＩＣ（株）製）０．００２ｇを、乳酸エチル１３．９ｇ及びプロピレングリコールモノメチルエーテル２６．３ｇに溶解させて溶液とした。その後、該溶液を孔径１．０μｍのＰＴＦＥ製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。 <Comparative Example 8>
8.0 g of the copolymer solution obtained in Synthesis Example 2, 0.8 g of tetramethoxymethyl glycol uryl (POWDERLINK® 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinkable compound, SP as a photoacid generator. -606 (manufactured by ADEKA Corporation) 0.028 g and MegaFvck (registered trademark) R-40 (manufactured by DIC Co., Ltd.) 0.002 g are dissolved in 13.9 g of ethyl lactate and 26.3 g of propylene glycol monomethyl ether. To make a solution. Then, the solution was filtered using a PTFE microfilter having a pore size of 1.0 μm to prepare a resin composition.
［耐溶剤性試験］
実施例１乃至実施例４及び比較例１乃至比較例８で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において１００℃で１分間ベークし、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）を用いて５００ｍＪ／ｃｍ２で露光し、さらに１００℃で９分間ベークし、膜厚０．２μｍの膜を形成した。これらの膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル、シクロヘキサノン及び２．３８質量％濃度の水酸化テトラメチルアンモニウム（以下、ＴＭＡＨと略称する。）水溶液に、それぞれ２３℃の温度条件下、５分間浸漬した後、１００℃で１分間乾燥ベークを行った。浸漬前の膜及び乾燥ベーク後の膜の膜厚測定を行い、下記式から膜厚変化率を算出した。
［１－（乾燥ベーク後の膜厚／浸漬前の膜厚）］×１００（％）
前記浸漬溶剤のうち１つでも膜厚変化率が１０％以上あった場合は“×”、全ての溶剤について膜厚変化率が１０％未満であった場合は“○”として耐溶剤性を評価した。評価結果を表１に示す。 [Solvent resistance test]
The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were each applied on a silicon wafer using a spin coater, baked on a hot plate at 100 ° C. for 1 minute, and i-ray. An exposure was made at 500 mJ / cm 2 using a stepper NSR-2205i12D (NA = 0.63) (manufactured by Nikon Corporation), and further baked at 100 ° C. for 9 minutes to form a film having a film thickness of 0.2 μm. For these films, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, cyclohexanone and tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) aqueous solution having a concentration of 2.38% by mass were added. After immersing for 5 minutes under the temperature conditions of 23 ° C., dry baking was performed at 100 ° C. for 1 minute. The film thickness of the film before immersion and the film thickness after drying baking were measured, and the film thickness change rate was calculated from the following formula.
[1- (Film thickness after dry baking / Film thickness before immersion)] x 100 (%)
The solvent resistance is evaluated as "x" when the film thickness change rate is 10% or more even for one of the immersion solvents, and as "○" when the film thickness change rate is less than 10% for all the solvents. did. The evaluation results are shown in Table 1.
［透過率測定］
実施例１乃至実施例４及び比較例１乃至比較例８で調製した樹脂組成物をそれぞれ、石英基板上にスピンコーターを用いて塗布し、ホットプレート上において１００℃で１分間ベークし、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）を用いて５００ｍＪ／ｃｍ２で露光し、さらに１００℃で９分間ベークし、膜厚０．２μｍの膜を形成した。これらの膜に対して、紫外線可視分光光度計ＵＶ－２５５０（（株）島津製作所製）を用いて、波長４００ｎｍ～８００ｎｍの範囲で波長を２ｎｍずつ変化させて透過率を測定した。波長４００ｎｍ～８００ｎｍの範囲で測定された最低透過率の値を表１に示す。 [Transmittance measurement]
The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were each applied on a quartz substrate using a spin coater, baked on a hot plate at 100 ° C. for 1 minute, and i-ray. It was exposed at 500 mJ / cm 2 using a stepper NSR-2205i12D (NA = 0.63) (manufactured by Nikon Corporation), and further baked at 100 ° C. for 9 minutes to form a film having a film thickness of 0.2 μm. The transmittance of these films was measured using an ultraviolet visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) by changing the wavelength by 2 nm in the wavelength range of 400 nm to 800 nm. Table 1 shows the values of the lowest transmittance measured in the wavelength range of 400 nm to 800 nm.
［信頼性試験］
実施例１乃至実施例４及び比較例２乃至比較例６で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において１００℃で１分間ベークし、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）を用いて５００ｍＪ／ｃｍ２で露光し、さらに１００℃で９分間ベークし、膜厚０．２μｍの膜を形成した。得られた膜を空気中で９０℃の条件に２４０時間曝し、信頼性試験を実施した。試験前後の膜の膜厚を、干渉膜厚計を用い測長した。下記式から膜厚変化率を算出し、膜厚変化率が５％を超える場合は“×”、５％以下の場合は“○”として評価した。評価結果を表１に示す。
［１－（試験後膜厚／試験前膜厚）］×１００（％） [Reliability test]
The resin compositions prepared in Examples 1 to 4 and Comparative Examples 2 to 6 were each applied on a silicon wafer using a spin coater, baked on a hot plate at 100 ° C. for 1 minute, and i-ray. An exposure was made at 500 mJ / cm 2 using a stepper NSR-2205i12D (NA = 0.63) (manufactured by Nikon Corporation), and further baked at 100 ° C. for 9 minutes to form a film having a film thickness of 0.2 μm. The obtained membrane was exposed to air at 90 ° C. for 240 hours, and a reliability test was carried out. The film thickness before and after the test was measured using an interference film thickness meter. The film thickness change rate was calculated from the following formula, and was evaluated as “x” when the film thickness change rate exceeded 5% and as “◯” when it was 5% or less. The evaluation results are shown in Table 1.
[1- (Film thickness after test / Film thickness before test)] x 100 (%)
［カラーレジスト残渣］
実施例１、実施例４及び比較例５乃至比較例８で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において１００℃で１分間、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）を用いて露光し、さらにホットプレート上において１００℃で９分間ベークし、膜厚０．２μｍのカラーフィルター下層膜を形成した。このカラーフィルター下層膜上に、顔料としてＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４及びＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７を含む、光ラジカル重合性顔料分散型赤色カラーレジスト液を塗布し、ホットプレート上において１００℃で１分間ベークを行い、膜厚０．５μｍの赤色カラーレジスト膜を形成した。次いで、ｉ線ステッパーＮＳＲ－２２０５ｉ１２Ｄ（ＮＡ＝０．６３）（（株）ニコン製）を用いて、前記赤色カラーレジスト膜を、マスクを介して露光し、２．３８質量％のＴＭＡＨ水溶液で６０秒間現像し、超純水で２０秒間リンス後、乾燥して、１００μｍ×１００μｍの矩形パターンを形成した。走査型電子顕微鏡Ｓ－９２６０（（株）日立ハイテクノロジーズ製）を用いて、矩形パターン周囲のカラーフィルター下層膜上の赤色カラーレジストの残渣を観察した。比較例６を基準として比較した際の残渣レベルの評価結果を、表１に示す。前記カラーフィルター下層膜上に観察される赤色カラーレジスト残渣が、比較例６よりも“少ない”、“多い”、“同等”の３レベルで、残渣レベルを評価した。 [Color resist residue]
The resin compositions prepared in Example 1, Example 4, and Comparative Examples 5 to 8 were each applied on a silicon wafer using a spin coater, and on a hot plate at 100 ° C. for 1 minute, the i-line stepper NSR. It was exposed with -2205i12D (NA = 0.63) (manufactured by Nikon Corporation) and further baked on a hot plate at 100 ° C. for 9 minutes to form a color filter underlayer film having a film thickness of 0.2 μm. On the underlayer film of this color filter, C.I. I. Pigment Red 254 and C.I. I. A photoradical polymerizable pigment-dispersed red color resist solution containing Pigment Red 177 was applied and baked on a hot plate at 100 ° C. for 1 minute to form a red color resist film having a thickness of 0.5 μm. Next, the red color resist film was exposed through a mask using an i-line stepper NSR-2205i12D (NA = 0.63) (manufactured by Nikon Corporation), and 60 in a 2.38 mass% TMAH aqueous solution. It was developed for seconds, rinsed with ultrapure water for 20 seconds, and then dried to form a rectangular pattern of 100 μm × 100 μm. Using a scanning electron microscope S-9260 (manufactured by Hitachi High-Technologies Corporation), the residue of the red color resist on the underlayer film of the color filter around the rectangular pattern was observed. Table 1 shows the evaluation results of the residue level when compared with Comparative Example 6 as a reference. The residue level of the red color resist residue observed on the underlayer film of the color filter was evaluated at three levels of "less", "more", and "equivalent" than in Comparative Example 6.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
表１の結果から、本発明の樹脂組成物から形成された膜は、高耐溶剤性かつ高透明性でであった。また、本発明の樹脂組成物から形成された膜上では、カラーレジストの残渣が少なく、本発明の樹脂組成物から形成された膜はカラーレジストの残渣の発生を抑える効果に優れるものであった。一方、比較例１で調製した樹脂組成物から形成された膜については高透明性であったが、耐溶剤性が不十分だった。比較例２乃至比較例４で調製した樹脂組成物から形成された膜については高耐溶剤性かつ高透明性であったが、信頼性が不十分だった。比較例５及び比較例６で調製した樹脂組成物から形成された膜については高耐溶剤性、高透明性かつ高信頼性であったが、残渣レベルが基準又は基準よりも多かった。比較例７で調製した樹脂組成物から形成された膜については高耐溶剤性かつ高透明性であったが、残渣レベルが基準と同等だった。比較例８で調製した樹脂組成物から形成された膜については高溶解性かつ高透明性であったが、残渣レベルが基準よりも多かった。 From the results shown in Table 1, the film formed from the resin composition of the present invention was highly solvent resistant and highly transparent. Further, on the film formed from the resin composition of the present invention, the residue of the color resist was small, and the film formed from the resin composition of the present invention was excellent in the effect of suppressing the generation of the residue of the color resist. .. On the other hand, the film formed from the resin composition prepared in Comparative Example 1 had high transparency, but its solvent resistance was insufficient. The films formed from the resin compositions prepared in Comparative Examples 2 to 4 had high solvent resistance and high transparency, but their reliability was insufficient. The films formed from the resin compositions prepared in Comparative Examples 5 and 6 had high solvent resistance, high transparency and high reliability, but the residue level was higher than the standard or standard. The film formed from the resin composition prepared in Comparative Example 7 had high solvent resistance and high transparency, but the residue level was equivalent to the standard. The film formed from the resin composition prepared in Comparative Example 8 was highly soluble and highly transparent, but the residue level was higher than the standard.
本発明の樹脂組成物は、ＣＣＤイメージセンサ、ＣＭＯＳイメージセンサ、液晶ディスプレイ、有機ＥＬディスプレイ等のデバイスにおける、カラーフィルター下層膜、カラーフィルター上層膜、フィラー分散レジスト下層膜等を形成する材料として好適である。また、本発明の樹脂組成物から形成されるカラーフィルター下層膜上にカラーレジストパターンを形成した場合、カラーレジストの残渣の発生を抑えることができ、カラーフィルターを備えたデバイスの品質及び歩留まりの向上に有用である。
  The resin composition of the present invention is suitable as a material for forming a color filter lower layer film, a color filter upper layer film, a filler dispersion resist lower layer film, and the like in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays. is there. Further, when a color resist pattern is formed on the color filter lower layer film formed from the resin composition of the present invention, the generation of color resist residue can be suppressed, and the quality and yield of the device provided with the color filter can be improved. It is useful for.

Claims (8)

  1. 下記式（１）で表される構造単位を有するホモポリマー、アルコキシアルキル基を１分子中に少なくとも２個有する架橋性化合物、光酸発生剤、界面活性剤、及び有機溶剤を含有し、
    前記架橋性化合物の含有量は前記ホモポリマーの含有量に対し４０質量％乃至６０質量％であり、前記光酸発生剤の含有量は前記ホモポリマー及び前記架橋性化合物の含有量の和に対し少なくとも０．８質量％である、樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （前記式中、Ｒ１は置換基としてヒドロキシ基を少なくとも１つ有する炭素原子数１乃至６のアルキル基を表す。）     It contains a homopolymer having a structural unit represented by the following formula (1), a crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant, and an organic solvent.
    The content of the crosslinkable compound is 40% by mass to 60% by mass with respect to the content of the homopolymer, and the content of the photoacid generator is the sum of the contents of the homopolymer and the crosslinkable compound. A resin composition which is at least 0.8% by mass.
    Figure JPOXMLDOC01-appb-C000001
     (In the above formula, R 1 represents an alkyl group having at least one hydroxy group as a substituent and having 1 to 6 carbon atoms.)
  2. 前記光酸発生剤から発生する酸は超酸であり、その酸解離定数ｐＫａは－７より小さい、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the acid generated from the photoacid generator is a superacid, and the acid dissociation constant pKa thereof is smaller than −7.
  3. 前記光酸発生剤から発生する酸はブレンステッド酸である、請求項１又は請求項２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the acid generated from the photoacid generator is Bronsted acid.
  4. 前記光酸発生剤はＮ－（トリフルオロメタンスルホニルオキシ）－１，８－ナフタルイミド又はその誘導体である、請求項１乃至請求項３のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the photoacid generator is N- (trifluoromethanesulfonyloxy) -1,8-naphthalimide or a derivative thereof.
  5. 前記光酸発生剤はジフェニル［４－（フェニルチオ）フェニル］スルホニウム塩化合物である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the photoacid generator is a diphenyl [4- (phenylthio) phenyl] sulfonium salt compound.
  6. 基材上に請求項１乃至請求項５のいずれか一項に記載の樹脂組成物を塗布する工程、
    該樹脂組成物を７５℃乃至１１０℃でプリベークし、近紫外線で露光後、７５℃乃至１１０℃でポストベークしてカラーフィルター下層膜を形成する工程、及び
    前記カラーフィルター下層膜上にカラーレジストを用いてカラーフィルターを形成する工程を有する、カラーフィルターを備えたデバイスの作製方法。     A step of applying the resin composition according to any one of claims 1 to 5 onto a base material.
    A step of prebaking the resin composition at 75 ° C. to 110 ° C., exposing it to near ultraviolet rays, and then post-baking it at 75 ° C. to 110 ° C. to form a color filter underlayer film, and applying a color resist on the color filter underlayer film. A method of making a device with a color filter, which comprises the step of forming a color filter using the color filter.
  7. 前記カラーフィルター上に前記樹脂組成物を塗布する工程、及び該樹脂組成物を７５℃乃至１１０℃でプリベークし、近紫外線で露光後、７５℃乃至１１０℃でポストベークしてカラーフィルター上層膜を形成する工程をさらに有する、請求項６に記載のカラーフィルターを備えたデバイスの作製方法。 The step of applying the resin composition on the color filter, and the resin composition is prebaked at 75 ° C. to 110 ° C., exposed to near ultraviolet rays, and then post-baked at 75 ° C. to 110 ° C. to form a color filter upper layer film. The method for producing a device including the color filter according to claim 6, further comprising a step of forming.
  8. 前記プリベーク及びポストベークは１００℃以下で行う、請求項６又は請求項７に記載のカラーフィルターを備えたデバイスの作製方法。
          The method for manufacturing a device having a color filter according to claim 6 or 7, wherein the pre-baking and post-baking are performed at 100 ° C. or lower.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005275380A (en) * 2004-02-23 2005-10-06 Nissan Chem Ind Ltd Dye-containing resist composition and color filter using the same
KR20150032418A (en) * 2013-09-17 2015-03-26 동우 화인켐 주식회사 A colored photosensitive resin composition, color filter and liquid crystal display device having the same
JP2015232607A (en) * 2014-06-09 2015-12-24 信越化学工業株式会社 Chemically amplified positive resist material and pattern forming method
WO2016013344A1 (en) * 2014-07-24 2016-01-28 日産化学工業株式会社 Resin composition for forming color filter underlayer film
WO2018033995A1 (en) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Curable resin composition for forming easily strippable film, and process for producing same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000344866A (en) 1999-06-07 2000-12-12 Jsr Corp Curable composition for flattened film, and flattened film
US7776504B2 (en) * 2004-02-23 2010-08-17 Nissan Chemical Industries, Ltd. Dye-containing resist composition and color filter using same
JP2008031370A (en) 2006-07-31 2008-02-14 Tokyo Ohka Kogyo Co Ltd Flattened film-forming composition
US9994685B2 (en) 2011-07-07 2018-06-12 Nissan Chemical Industries, Ltd. Resin composition
TWI720168B (en) * 2016-03-30 2021-03-01 日商日產化學工業股份有限公司 A resist underlayer film forming composition containing a compound with a glycoluril skeleton as an additive
US11282911B2 (en) 2016-05-24 2022-03-22 Sony Group Corporation Display device, display module, method of manufacturing display device, and method of manufacturing display module

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005275380A (en) * 2004-02-23 2005-10-06 Nissan Chem Ind Ltd Dye-containing resist composition and color filter using the same
KR20150032418A (en) * 2013-09-17 2015-03-26 동우 화인켐 주식회사 A colored photosensitive resin composition, color filter and liquid crystal display device having the same
JP2015232607A (en) * 2014-06-09 2015-12-24 信越化学工業株式会社 Chemically amplified positive resist material and pattern forming method
WO2016013344A1 (en) * 2014-07-24 2016-01-28 日産化学工業株式会社 Resin composition for forming color filter underlayer film
WO2018033995A1 (en) * 2016-08-19 2018-02-22 大阪有機化学工業株式会社 Curable resin composition for forming easily strippable film, and process for producing same

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