WO2014192671A1 - Composition de résine photosensible, photoespaceur, film protecteur pour filtres colorés et film protecteur ou film isolant d'écran tactile - Google Patents

Composition de résine photosensible, photoespaceur, film protecteur pour filtres colorés et film protecteur ou film isolant d'écran tactile Download PDF

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Publication number
WO2014192671A1
WO2014192671A1 PCT/JP2014/063779 JP2014063779W WO2014192671A1 WO 2014192671 A1 WO2014192671 A1 WO 2014192671A1 JP 2014063779 W JP2014063779 W JP 2014063779W WO 2014192671 A1 WO2014192671 A1 WO 2014192671A1
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group
meth
carbon atoms
photosensitive resin
resin composition
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PCT/JP2014/063779
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English (en)
Japanese (ja)
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真友子 山下
優 酒井
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三洋化成工業株式会社
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Priority to JP2015519839A priority Critical patent/JP6377056B2/ja
Priority to CN201480026139.1A priority patent/CN105190440B/zh
Priority to KR1020157032058A priority patent/KR102326631B1/ko
Publication of WO2014192671A1 publication Critical patent/WO2014192671A1/fr

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    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133519—Overcoatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties

Definitions

  • the present invention relates to a photosensitive resin composition. Specifically, the present invention relates to a photosensitive resin composition suitable for a photo spacer, a protective film for a color filter, a protective film for a touch panel, or an insulating film for a touch panel.
  • liquid crystal display devices have attracted attention, and photosensitive resins are frequently used in the manufacturing process.
  • a photosensitive resin in which a color pigment is dispersed is used for a portion corresponding to a pixel on a color filter, and a photosensitive resin is also used for a black matrix.
  • beads having a predetermined particle size are used as a photo spacer, and a gap is provided between two substrates.
  • these beads are dispersed randomly, there is a problem that light leakage, scattering of incident light, etc. occur due to distribution on the color display pixels, and the contrast of the liquid crystal panel is lowered.
  • a method has been proposed in which a columnar resinous spacer is formed on a black matrix located between pixels by a photolithographic method of partial pattern exposure and development using a photosensitive resin. . Since the photo spacer can be arranged at a position avoiding the pixels, it does not adversely affect the display quality as described above, and the display quality can be improved.
  • a drop method (ODF: One Drop Fill) has been proposed in place of the conventional liquid crystal inflow method (vacuum suction method) as the mother glass for manufacturing a liquid crystal display (LCD) becomes larger.
  • ODF liquid crystal inflow method
  • the number of steps and the process time can be reduced as compared with the conventional vacuum suction method.
  • a predetermined amount of liquid crystal calculated from the cell gap is dropped and held, so that a pressure change is applied to the photo spacer arranged on the glass substrate. It is desired for the photo spacer to have a high elastic recovery characteristic so that the shape does not plastically deform with respect to this pressure change.
  • a method of nano-dispersing inorganic fine particles such as organosilica sol (for example, Patent Document 2), or a content ratio of a polyfunctional monomer such as dipentaerythritol hexaacrylate is 50% or more.
  • a method for example, Patent Document 3 is known in which high elasticity is obtained by increasing the thickness.
  • the resin composition becomes hydrophobic, there is a problem that the development time becomes long and the productivity is lowered, and a photosensitive resin composition capable of achieving both high elasticity and high developability is obtained. It is not done.
  • An object of the present invention is to provide a photosensitive resin composition that is highly developable, has a cured product with excellent elastic recovery characteristics and adhesion, and can form a high-definition spacer.
  • the present invention includes a hydrophilic resin (A), a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), a solvent (D) having an HLB of 8.0 to 30.0, and the following: A photosensitive resin composition containing a compound (E) which is a condensate containing the compound represented by the general formula (1) as an essential constituent monomer; and the photosensitive resin composition is irradiated with light and then alkali-developed.
  • a photo spacer, a color filter protective film, and a touch panel protective film or insulating film formed by patterning and post-baking.
  • R 1 is one selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group whose alkyl group has 1 to 6 carbon atoms
  • R 2 is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • M is a silicon atom
  • It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms
  • m is 0 or 1.
  • the photosensitive resin composition of the present invention has high developability, the cured product has excellent elastic recovery properties, excellent adhesion to a glass substrate, and can form a high-definition photospacer. There is an effect.
  • the photosensitive resin composition of the present invention comprises a hydrophilic resin (A), a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), a solvent having an HLB of 8.0 to 30.0 (D ) And a compound (E), which is a condensate containing the compound represented by the following general formula (1) as an essential constituent monomer, as an essential component.
  • R 1 is one selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group whose alkyl group has 1 to 6 carbon atoms
  • R 2 is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • M is a silicon atom
  • It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms
  • m is 0 or 1.
  • (meth) acrylate means “acrylate and / or methacrylate”
  • (meth) acrylic acid means “acrylic acid and / or methacrylic acid”
  • (meth) acrylic resin means “(Acrylic resin and / or methacrylic resin)
  • (meth) acryloyl group means “acryloyl group and / or methacryloyl group”
  • (meth) acryloyloxy group means "acryloyloxy group and / or methacrylic group”.
  • hydrophilic resin (A) used in the present invention examples include a hydrophilic vinyl resin (A1), a hydrophilic epoxy resin (A2), a hydrophilic polyester resin, a hydrophilic polyamide resin, a hydrophilic polycarbonate resin, and a hydrophilic polyurethane resin. Can be mentioned. (A) may use 1 type and may use 2 or more types together. Among these, the hydrophilic vinyl resin (A1) and the hydrophilic epoxy resin (A2) are preferable from the viewpoint of the sensitivity of the photosensitive resin composition and the viewpoint of ease of production. From the viewpoint of elastic recovery characteristics, a hydrophilic epoxy resin (A2) is more preferable.
  • the hydrophilicity index in the hydrophilic resin (A) is defined by HLB. Generally, the larger this value, the higher the hydrophilicity.
  • the HLB value of (A) is preferably 4 to 19, more preferably 5 to 18, particularly preferably 6 to 17. When it is 4 or more, the developing property is further improved when developing the photospacer, and when it is 19 or less, the water resistance of the cured product is further improved.
  • HLB is an index indicating a balance between hydrophilicity and lipophilicity, and is described in, for example, “Introduction to Surfactants” (published by Sanyo Chemical Industries, Ltd., 2007, Takehiko Fujimoto), page 212. It is known as the calculated value by the Oda method, not the calculated value by the Griffin method.
  • the organic value and the inorganic value for deriving HLB can be calculated using the values in the table described in the above “Introduction to Surfactant” page 213. However, the oxyethylene group (—CH 2 CH 2 O—) is treated specially and calculated using an inorganic value of 75 and an organic value of 40.
  • the solubility parameter (hereinafter referred to as SP value) [(unit is (cal / cm 3 ) 1/2 ]) of the hydrophilic resin (A) is preferably 7 to 14, more preferably 8 to 13, particularly preferably. Is from 9 to 13. If it is 7 or more, the developability can be further improved, and if it is 14 or less, the water resistance of the cured product is further improved.
  • the SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al. "POLYMER ENFINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors (pp. 147-154)" Those with close SP values are likely to mix with each other (highly dispersible), and those with a distant numerical value are difficult to mix.
  • hydrophilic group examples include a carboxyl group, a hydroxyl group, an amino group, an amide group, a polyether group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group.
  • a carboxyl group is preferred from the viewpoint of alkali developability.
  • the carboxyl group content is indicated by an acid value.
  • the acid value of (A) is preferably 10 to 500 mgKOH / g, more preferably 20 to 300 mgKOH / g. If it is 10 mgKOH / g or more, the developability is more likely to be exhibited, and if it is 500 mgKOH / g or less, the water resistance of the cured product can be further improved.
  • the acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution.
  • the method is as follows. (I) About 0.1 to 10 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then a neutral methanol / acetone solution [a mixture of acetone and methanol at 1: 1 (volume ratio)] is added and dissolved. (Ii) Add several drops of phenolphthalein indicator and titrate with 0.1 mol / L potassium hydroxide titration solution. The end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds. (Iii) Determine using the following equation.
  • Acid value (mgKOH / g) (A ⁇ f ⁇ 5.61) / S
  • f titer of 0.1 mol / L potassium hydroxide titration solution
  • S sampling amount (g)
  • hydrophilic resins (A) examples include those having the above-mentioned hydrophilic group in the side chain and / or terminal of the vinyl polymer molecule.
  • a preferred production method of (A1) is a method of vinyl polymerizing a vinyl monomer (a) having a hydrophilic group and, if necessary, a hydrophobic group-containing vinyl monomer (b).
  • Examples of the vinyl monomer (a) having a hydrophilic group include the following vinyl monomers (a1) to (a7).
  • (A) may use 1 type and may use 2 or more types together.
  • Hydroxyl-containing vinyl monomer Hydroxyalkyl (meth) acrylates having 1 to 30 carbon atoms in the hydroxyalkyl group (such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate)), polyalkylenes ( Alkylene group having 1 to 8 carbon atoms) glycol (degree of polymerization 2 to 40) mono (meth) acrylate [polyethylene glycol mono (meth) acrylate etc.], alkylol (meth) acrylamide [N-methylol (meth) acrylamide etc.], Examples thereof include hydroxystyrene and 2-hydroxyethylpropenyl ether.
  • (A3) Sulphonic acid group-containing vinyl monomer examples thereof include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, ⁇ -methyl styrene sulfonic acid, 2- (meth) acryloylamido-2-methylpropane sulfonic acid, and salts thereof.
  • the salt include alkali metal (sodium and potassium) salts, alkaline earth metal (calcium and magnesium) salts, primary to tertiary amine salts, ammonium salts and quaternary ammonium salts.
  • (A4) Amino group-containing vinyl monomer: And tertiary amino group-containing (meth) acrylates [dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate)] and the like.
  • (A5) Amide group-containing vinyl monomer: (Meth) acrylamide, N-alkyl (1 to 6 carbon atoms) (meth) acrylamide, diacetone acrylamide, N, N′-methylene-bis (meth) acrylamide, N, N-dialkyl (1 to 6 carbon atoms) or N, N-diaralkyl (C7-15) (meth) acrylamide (eg, N, N-dimethylacrylamide and N, N-dibenzylacrylamide), methacrylformamide, N-methyl-N-vinylacetamide, cinnamic acid Examples include amides and cyclic amides (N-vinylpyrrolidone, N-allylpyrrolidone, etc.).
  • Quaternary ammonium base-containing vinyl monomer A quaternized product of a tertiary amino group-containing vinyl monomer having 6 to 50 carbon atoms (preferably 8 to 20 carbon atoms) (for example, methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.) such as dimethyl
  • (A7) (Poly) ether group-containing vinyl monomer Alkoxy (alkoxy group having 1 to 8 carbon atoms) alkylene (alkylene group having 1 to 8 carbon atoms) glycol mono (meth) acrylate [methoxyethylene glycol mono (meth) acrylate and methoxypropylene glycol mono (meth) acrylate, etc.], alkoxy (Alkoxy group having 1 to 8 carbon atoms) polyalkylene (alkylene group having 2 to 4 carbon atoms) glycol mono (meth) acrylate [methoxypolyethylene glycol (degree of polymerization 2 to 40) mono (meth) acrylate and methoxypolypropylene glycol (polymerization) Degree 2 to 30) mono (meth) acrylate, etc.].
  • hydrophobic group-containing vinyl monomer (b) used in combination with the hydrophilic group-containing vinyl monomer (a) in the hydrophilic vinyl polymer (A1) as necessary include the following monomers (b1) to (b5).
  • (B) may use 1 type and may use 2 or more types together.
  • (B1) (Meth) acrylic acid ester:
  • alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • Examples of the alicyclic group-containing (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate.
  • Aromatic hydrocarbon monomer examples include styrene, ⁇ -methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, and vinyl naphthalene. It is done.
  • Carboxylic acid vinyl ester examples of those having 4 to 50 carbon atoms include vinyl acetate, vinyl propionate and vinyl butyrate.
  • Vinyl ether monomer examples of those having 3 to 50 carbon atoms (preferably 6 to 20 carbon atoms) include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl butyl ether.
  • Vinyl ketone monomer examples of those having 4 to 50 carbon atoms include vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone.
  • the hydrophilic vinyl resin (A1) is a polymer having (a) and (b) as a constituent monomer as described above, and a (meth) acryloyl group as a side chain or a terminal as necessary for the purpose of further improving sensitivity. You may make it contain.
  • Examples of the method for containing a (meth) acryloyl group in the side chain include the following methods (1) and (2).
  • a polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (a), and then (meth) A method of reacting a compound having an acryloyl group and an isocyanate group (such as acryloylethyl isocyanate).
  • an isocyanate group such as a hydroxyl group or a primary or secondary amino group
  • a polymer is produced using a monomer having a group capable of reacting with an epoxy group (hydroxyl group, carboxyl group, primary or secondary amino group, etc.) in at least a part of (a), and then A method of reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl (meth) acrylate).
  • the number average molecular weight of the hydrophilic vinyl resin (A1) by gel permeation chromatography (GPC) is preferably 1,000 to 30,000, more preferably Is 1,500 to 10,000.
  • the Mn of the hydrophilic resin (A) in the present invention is determined using a GPC measuring device (HLC-8120GPC, manufactured by Tosoh Corporation), a column (TSKgel GMHXL 2 + TSKgel Multipore HXL-M, manufactured by Tosoh Corporation). , Measured in a THF solvent at a measurement temperature of 40 ° C. using TSK standard polystyrene [manufactured by Tosoh Corporation] as a reference substance.
  • the hydrophilic epoxy resin (A2) is an epoxy resin containing a hydrophilic functional group such as a hydroxyl group, a carboxyl group, or an oxyethylene group in the molecule.
  • (A2) preferably has a (meth) acryloyl group in the molecule from the viewpoint of photocuring reactivity.
  • a preferred method for producing the hydrophilic epoxy resin (A2) is that the epoxy group in the raw material epoxy resin (A2 0 ) (hereinafter sometimes simply referred to as (A2 0 )) contains a (meth) acryloyl group-containing monomer.
  • Carboxylic acid (a21) is reacted to open an epoxy group to form a hydroxyl group to form a (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 0 ).
  • the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) is reacted.
  • (meth) acryloyl group containing monocarboxylic acid (a21) is unsaturated monocarboxylic acid containing a (meth) acryloyl group among carboxyl group-containing vinyl monomers (a2).
  • raw material epoxy resin (A2 0 ) examples include aliphatic epoxy resins [eg, Etototo YH-300, PG-202, PG-207 (all manufactured by Toto Kasei Co., Ltd.)] and alicyclic epoxy resins [eg, CY-179.
  • aromatic epoxy resins for example, phenol novolac epoxy resin, cresol novolac epoxy resin [for example, EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.)] Bisphenol A epoxy resin, biphenyl type epoxy resin, glycidyl-modified polyvinylphenol, etc.].
  • aromatic epoxy resin is preferable from the viewpoint of hardness.
  • polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) used in the production of (A2) include unsaturated polyvalent carboxylic acids and their anhydrides, and saturated polyvalent (2-6 valent) carboxylic acids (For example, aliphatic saturated polyvalent carboxylic acids such as oxalic acid, succinic acid, phthalic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid; tetrahydrophthalic acid, hexahydro Aromatic or cycloaliphatic polycarboxylic acids such as phthalic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid) and their anhydrides (for example, succinic anhydride, Alipha
  • the charged weight ratio of (meth) acryloyl group-containing monocarboxylic acid (a21) / (A2 0 ) is preferably such that the concentration of (meth) acryloyl groups in (A2) is 1.0 mmol / g or more.
  • the weight ratio is such that
  • the reaction temperature in the reaction between (A2 0 ) and (a21) is not particularly limited, but is preferably 70 to 110 ° C.
  • the reaction time is not particularly limited, but is preferably 5 to 30 hours.
  • a catalyst for example, triphenylphosphine
  • a radical polymerization inhibitor hydroquinone, p-methoxyphenol, etc.
  • the charge equivalent of the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) relative to the weight of the (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 0 ) is such that the acid value of (A2) is Equivalent / g so as to be 10 to 500 mg KOH / g.
  • the charge equivalent of (c) / (A2 0 ) (meth) acrylic acid adduct is preferably 0 from the above viewpoint. .18 to 8.9 meq / g, more preferably 0.53 to 7.1 meq / g.
  • the reaction temperature in the reaction of the (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 0 ) with the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) is not particularly limited, but preferably 70 ⁇ 110 ° C.
  • the reaction time is not particularly limited, but is preferably 3 to 10 hours.
  • the number average molecular weight of (A2) is preferably 500 to 3,000, more preferably 1,000 to 2,800, from the viewpoints of sensitivity and developability as the photosensitive resin composition.
  • Photosensitive resin composition hydrophilic resin (A), polyfunctional (meth) acrylate (B), photopolymerization initiator (C) and compound (E) [hereinafter (A) to (C), (E) and Describe. ]
  • the content of (A) based on the total weight is preferably 10 to 80% by weight, more preferably 15 to 78% by weight, and particularly preferably 20 to 75% by weight. If it is 10% by weight or more, the alkali developability can be exhibited satisfactorily, and if it is 80% by weight or less, the elastic recovery property can be exhibited more satisfactorily.
  • any known polyfunctional (meth) acrylate can be used without particular limitation. Examples thereof include meth) acrylate (B1), trifunctional (meth) acrylate (B2), and 4-6 functional (meth) acrylate (B3). (B) may use 1 type and may use 2 or more types together.
  • bifunctional (meth) acrylate means that the number of (meth) acryloyl groups is two, and the same description method is used hereinafter.
  • Examples of the bifunctional (meth) acrylate (B1) include esterified products of polyhydric (preferably divalent to octavalent) alcohol having 2 to 30 carbon atoms and (meth) acrylic acid [for example, di (meth) acrylate of ethylene glycol, Di (meth) acrylate of glycerin, di (meth) acrylate of trimethylolpropane, di (meth) acrylate of 3-hydroxy-1,5-pentanediol, 2-hydroxy-2-ethyl-1,3-propanediol Di (meth) acrylate]; an alkylene oxide (2 to 4 carbon atoms of an alkylene group) of a polyhydric (preferably divalent to octavalent) alcohol having 2 to 30 carbon atoms and an adduct of (meth) acrylic acid Esterified products [for example, di (meth) acrylate of trimethylolpropane ethylene oxide adduct, glycerin Di (me
  • Examples of the trifunctional (meth) acrylate (B2) include tri- or higher-valent (preferably tri- to 8-valent) alcohol having 3 to 30 carbon atoms and esterified product of (meth) acrylic acid [for example, tri (meth) acrylate, A tri (meth) acrylate of methylolpropane, a tri (meth) acrylate of pentaerythritol]; and an alkylene oxide of 3 to 30 (preferably 3 to 8) carbon atoms having 3 to 30 carbon atoms (2 to 3 carbon atoms of the alkylene group). 4) 1-30 mol adduct and esterified product of (meth) acrylic acid [for example, tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane] and the like.
  • Examples of the 4- to 6-functional (meth) acrylate (B3) include esterified products of a tetravalent or higher (preferably 4- to 8-valent) alcohol having 5 to 30 carbon atoms and (meth) acrylic acid [for example, tetra (meth) of pentaerythritol Acrylate, penta (meth) acrylate of dipentaerythritol, and hexa (meth) acrylate of dipentaerythritol]; and alkylene oxides of alkylene having 5 to 30 carbon atoms (preferably 4 to 8 valences) Carbonate 2-4) 1-30 mol adduct and esterified product of (meth) acrylic acid [for example, tetra (meth) acrylate of ethylene oxide adduct of dipentaerythritol, penta (meth) acrylate of ethylene oxide adduct of dipentaerythritol ) Pro of acrylate and dipentaery
  • (B2) and (B3) are preferable, and (B3) is more preferable.
  • Examples of (B) that can be easily obtained from the market include light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd .: pentaerythritol triacrylate), neomer DA-600 (manufactured by Sanyo Chemical Industries, Ltd .: dipentaerythritol pentaacrylate), and neomer. And EA-300 (manufactured by Sanyo Chemical Industries, Ltd .: pentaerythritol tetraacrylate).
  • the polyfunctional (meth) acrylate (B) used by this invention may contain the photosensitive acrylic oligomer (B4) in the one part.
  • examples of such (B4) include urethane acrylate, polyester acrylate, and polyether acrylate that have Mn of 1,000 or less, do not contain a carboxyl group, and have two or more acryloyl groups in one molecule. It is.
  • the content of the polyfunctional (meth) acrylate (B) in the photosensitive resin composition of the present invention is preferably based on the total weight of (A) to (C) and (E) from the viewpoint of the elastic recovery rate. Is 10 to 80% by weight, more preferably 15 to 75% by weight.
  • the photopolymerization initiator (C) used in the photosensitive resin composition of the present invention starts polymerization of a polymerizable unsaturated compound by exposure to radiation such as visible light, ultraviolet light, far infrared light, charged particle beam, and X-ray. Any component may be used as long as it can generate radicals that can be generated.
  • Examples of such a photopolymerization initiator (C) include acetophenone derivative (C1), acylphosphine oxide derivative (C2), titanocene derivative (C3), triazine derivative (C4), bisimidazole derivative (C5), O -Acyl oxime (oxime ester) derivative (C6), benzophenone derivative (C7), thioxanthone derivative (C8), ⁇ -diketone derivative (C9), anthraquinone derivative (C10), acridine derivative (C11), and two or more of these The mixture which contains is mentioned.
  • Examples of the acetophenone derivative (C1) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2 -Methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, dimethylbenzyl ketal, methylbenzoyl formate, 2-benzyl-2-dimethylamino-1- (4-morpholine Phenyl) - butan-1-one] and the like.
  • acylphosphine oxide derivative (C2) examples include trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • titanocene derivative (C3) examples include bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned.
  • Examples of the triazine derivative (C4) include trichloromethyltriazine and benzyl-2,4,6- (trihalomethyl) triazine.
  • Examples of the bisimidazole derivative (C5) include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer.
  • O-acyloxime (oxime ester) derivative (C6) examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
  • benzophenone derivative (C7) examples include benzophenone, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, and Michler's ketone.
  • Examples of the thioxanthone derivative (C8) include isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and diisopropylthioxanthone.
  • Examples of the ⁇ -diketone derivative (C9) include camphorquinone.
  • anthraquinone derivative (C10) examples include anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, and tert-butylanthraquinone.
  • Examples of the acridine derivative (C11) include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, and 1,3-bis (9-acridinyl) propane. Is mentioned.
  • (C1) to (C11), (C1), (C2), and (C8) are preferable from the viewpoint of ease of synthesis, and 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2, 4-Diethylthioxanthone is more preferable, and from the viewpoint of reactivity, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide is particularly preferred.
  • the photopolymerization initiator (C) As the photopolymerization initiator (C), a commercially available one can be easily obtained.
  • Irgacure 907 BASF
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one include Irgacure 369 (BASF)
  • Phenylphosphine oxide includes Irgacure 819 (manufactured by BASF)
  • 2,4-diethylthioxanthone includes Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.).
  • the content of the photopolymerization initiator (C) based on the total weight of (A) to (C) and (E) in the photosensitive resin composition of the present invention is preferably 2 to 15% by weight, more preferably 3 -12% by weight, particularly preferably 4-11% by weight. If it is 2% by weight or more, curing reactivity and elastic recovery characteristics can be exhibited more satisfactorily, and if it is 15% by weight or less, reduction of mask contamination at the time of light exposure can be further exhibited.
  • the photosensitive resin composition of the present invention contains a solvent (D) having an HLB of 8.0 or more and 30.0 or less as a fourth essential component. If the solvent (D) is not included, developability becomes insufficient.
  • the HLB of the solvent (D) is 8.0 or more and 30.0 or less, preferably 9.0 or more and 25.0 or less, more preferably 10.0 or more and 20.0 or less. If the HLB is less than 8.0, the developability deteriorates, and if it exceeds 30.0, the development adhesion deteriorates.
  • ether solvents including ether ester solvents and ether alcohol solvents
  • ethylene glycol dimethyl ether HLB: 11.9
  • ethylene glycol monomethyl ether HLB: 21.9
  • ethylene glycol monomethyl ether acetate HLB: 13.5
  • ethylene glycol monobutyl ether HLB: 14.6
  • diethylene glycol dimethyl ether HLB: 14.2
  • diethylene glycol diethyl ether HLB: 10.
  • diethylene glycol ethyl methyl ether HLB: 12.1, diethylene glycol monomethyl ether (HLB: 25.0), diethylene glycol monoethyl ether (H B: 20.8), diethylene glycol isopropyl methyl ether (HLB: 11.3), diethylene glycol monobutyl ether (HLB: 15.6), diethylene glycol monoethyl ether acetate (HLB: 13.1), triethylene glycol dimethyl ether (HLB: 14.1), tetraethylene glycol dimethyl ether (HLB: 15.0), propylene glycol monomethyl ether (HLB: 17.1), propylene glycol monoethyl ether (HLB: 13.3), propylene glycol propyl ether (HLB: 10) .9), dipropylene glycol monomethyl ether (HLB: 10.0), tripropylene glycol monomethyl ether (HLB: 9.4), 3-methoxybutanol (H B: 17.1) and 3-methoxybutan
  • ether solvents and ester solvents are preferable from the viewpoint of coatability.
  • diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutanol, and ethyl lactate. (D) may use 1 type and may use 2 or more types together.
  • the solvent (D) is a “water-soluble solvent”, and the term “water-soluble solvent” here refers to a glass flask containing pure water and solvent in a volume ratio of 1: 1, and then stirred at 25 ° C. for 5 minutes. Then, after standing for 10 minutes after stopping the stirring, when visually confirmed, the pure water and the solvent are not separated into two layers, and the mixed solution of water and the solvent is uniformly transparent.
  • the solvent is capable of dissolving or dispersing each component, and is selected according to the method of using the photosensitive resin composition of the present invention, and a solvent having a boiling point in the range of 100 to 280 ° C. is selected. Is preferred.
  • a solvent (F) other than the solvent (D) may be contained.
  • solvents (F) include ketone solvents (such as cyclohexanone), ether solvents (including ether ester solvents and ether alcohol solvents) (such as propylene glycol monomethyl ether acetate and methoxybutyl acetate), and ester solvents (such as butyl acetate). Etc. Among these, ether solvents and ester solvents are preferable from the viewpoint of coatability. (F) may use 1 type and may use 2 or more types together.
  • the content of the solvent (D) is preferably 5% by weight or more based on the total weight of (A) to (E), more preferably 8 to 90% by weight, particularly preferably 10 to 89% by weight, and most preferably 15%. ⁇ 88% by weight.
  • the content of the solvent (F) is preferably 0 to 95% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 95% by weight with respect to the weight of the solvent (D). *
  • the photosensitive resin composition of the present invention contains a compound (E) that is a condensate containing a compound represented by the following general formula (1) as an essential constituent monomer as a fifth essential component.
  • R 1 is one selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group whose alkyl group has 1 to 6 carbon atoms
  • R 2 is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • M is a silicon atom
  • It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms
  • m is 0 or 1.
  • a silicon atom and a titanium atom are preferable, and a silicon atom is more preferable.
  • examples of the aliphatic saturated hydrocarbon group include a linear alkyl group, a branched alkyl group, and an alicyclic saturated hydrocarbon group.
  • the straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-octyl and n-dodecyl groups and their deuterium substitutes;
  • the branched alkyl groups include isopropyl, isobutyl, sec-butyl and 2
  • Examples of the cyclic saturated hydrocarbon group include a cyclohexyl group, a cyclooctyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and a methylcyclohexyl group.
  • aromatic hydrocarbon group examples include an aryl group, an aralkyl group, and an alkylaryl group.
  • Aryl groups include phenyl, biphenyl, naphthyl groups and their deuterium, fluorine or chlorine substituents; aralkyl groups include tolyl, xylyl, mesityl and their deuterium, fluorine or chloride; and alkylaryl Groups include methylphenyl and ethylphenyl groups.
  • R 2 is preferably a linear alkyl group, branched alkyl group and aryl group from the viewpoint of curing reactivity, more preferably a linear alkyl group and an aryl group, particularly preferably a methyl group, an ethyl group, A phenyl group and a combination thereof.
  • R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group, and preferably a methyl group and an ethyl group from the viewpoint of thermosetting reactivity. is there.
  • examples of the compound having a (meth) acryloyloxyalkyl group as R 1 include the following compounds.
  • m is 0, that is, trifunctional compound having three alkoxy groups: 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyl Leuoxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxytitanium, 3-methacryloyloxypropyltrimethoxyaluminum, 3-methacryloyloxypropyltrimethoxyzirconium and the like.
  • m is 1, that is, a trifunctional compound having two alkoxy groups: 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3- Acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxytitanium, 3-methacryloyloxypropylmethyldimethoxyaluminum, 3-methacryloyloxypropylmethyldimethoxyzirconium and the like.
  • Examples of the compound having a glycidoxyalkyl group as R 1 include the following compounds.
  • m is 0, that is, a trifunctional compound having three alkoxy groups: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxytitanium, etc.
  • m is 1, that is, trifunctional compound having two alkoxy groups: 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxytitanium, 3- Glycidoxypropylmethyldimethoxyaluminum, 3-glycidoxypropylmethyldimethoxyzirconium, etc.
  • Examples of the compound having a mercaptoalkyl group as R 1 include the following compounds.
  • m is 0, that is, trifunctional compound having three alkoxy groups: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxytitanium, 3-mercaptopropyltrimethoxyaluminum, 3 -Mercaptopropyltrimethoxyzirconium and the like.
  • m is 1, that is, trifunctional compound having two alkoxy groups: 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxytitanium, 3-mercaptopropylmethyldimethoxyaluminum, 3-mercaptopropylmethyldimethoxyzirconium and the like.
  • Examples of the compound having an aminoalkyl group as R 1 include the following compounds.
  • m is 0, that is, trifunctional compound having three alkoxy groups: N-2 aminoethyl ⁇ -aminopropyltrimethoxysilane, N-2 aminoethyl ⁇ -aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, N-2 aminoethyl ⁇ -aminopropyltrimethoxytitanium, N-2 aminoethyl ⁇ -aminopropyltrimethoxyaluminum, N-2 aminoethyl ⁇ -aminopropyltrimethoxyzirconium and the like.
  • m is 1, that is, trifunctional compound having two alkoxy groups: N-2 aminoethyl ⁇ -aminopropylmethyldimethoxysilane, N-2 aminoethyl ⁇ -aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxy Silane, 3-aminopropylmethyldiethoxysilane, N-2aminoethyl ⁇ -aminopropylmethyldimethoxytitanium, N-2aminoethyl ⁇ -aminopropylmethyldimethoxyaluminum, N-2aminoethyl ⁇ -aminopropylmethyldimethoxyzirconium, etc. .
  • (meth) acrylic having 3 alkoxy groups is preferable.
  • a condensate comprising a leuoxyalkyl group-containing trifunctional silane compound as an essential constituent monomer, and a condensate comprising a glycidoxyalkyl group-containing trifunctional silane compound having three alkoxy groups as an essential constituent monomer More preferred are condensates containing 3-acryloyloxypropyltrimethoxysilane as an essential constituent monomer and condensates containing 3-glycidoxypropyltrimethoxysilane as an essential constituent monomer.
  • a dialkyl dialkoxysilane eg, dimethyldimethoxysilane, diethyldimethoxysilane, etc.
  • diaryl dialkoxy Silane for example, diphenyldimethoxysilane etc.
  • Examples of (E) that can be easily obtained from the market include KR-513 [manufactured by Shin-Etsu Chemical Co., Ltd .: acrylic group and methyl group-containing methoxysiloxane (acrylic-modified alkoxypolysiloxane)].
  • the content of the compound (E) is 0.1 to 20% by weight, preferably 0.5%, based on the total weight of (A) to (C) and (E), from the viewpoints of elastic recovery and adhesion. -15% by weight, more preferably 1-12% by weight.
  • the photosensitive resin composition of the present invention may further contain other components as necessary, and examples thereof include inorganic fine particles, a surfactant, a silane coupling agent, an antioxidant, and a polymerization inhibitor.
  • the total addition amount of the other components is 0 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.3 to 5% based on the total weight of (A) to (C) and (E). % By weight.
  • metal oxides and metal salts can be used as the inorganic fine particles.
  • the metal oxide include titanium oxide, silicon oxide, and aluminum oxide.
  • the metal salt include calcium carbonate and barium sulfate. Of these, metal oxides are preferable and silicon oxide is more preferable from the viewpoints of heat-resistant transparency and chemical resistance.
  • the inorganic fine particles preferably have a volume average primary particle diameter of 1 to 200 nm.
  • surfactant various types of surfactants such as anionic, cationic, nonionic, amphoteric, fluorine and silicon can be used. Of these, fluorine-based and silicon-based surfactants are preferable from the viewpoint of applicability.
  • silane coupling agent examples include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like.
  • Antioxidants include 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3-t-butyl- 4-hydroxy-5-methylphenyl) propoxy] -2,4,6,10-tetra-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3-4′-hydroxy-3 ′ -5'-di-t-butylphenyl) propionic acid-n-octadecyl, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 3,9-bis [2- [ 3- (3-
  • polymerization inhibitor examples include p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl-p-cresol and the like.
  • the photosensitive resin composition of the present invention can be obtained, for example, by mixing the above-described components with a known mixing apparatus such as a planetary mixer.
  • the photosensitive resin composition is usually liquid at room temperature, and its viscosity is 25 ° C., preferably 0.1 to 10,000 mPa ⁇ s, more preferably 1 to 8,000 mPa ⁇ s.
  • the photosensitive resin composition of the present invention is excellent in elastic recovery characteristics and high developability, and has high resolution. Therefore, the photo spacer, the protective film for the color filter, the protective film for the touch panel, or the insulating film for the touch panel Suitable as a photosensitive resin composition for film formation.
  • a preferable forming step of obtaining a cured product from the photosensitive resin composition of the present invention is a step of applying a photosensitive resin composition on a substrate, irradiating with light, forming a pattern by alkali development, and performing post-baking. .
  • the formation of the cured product is usually performed in the following steps (1) to (5).
  • substrate examples include roll coating, spin coating, spray coating, and slit coating.
  • the coating device examples include spin coater, air knife coater, roll coater, bar coater, die coater, curtain coater, gravure coater, and comma coater. Etc.
  • the film thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the drying temperature is preferably 20 to 120 ° C, more preferably 30 to 110 ° C.
  • the drying time is preferably 0.5 to 10 minutes, more preferably 1 to 8 minutes, and particularly preferably 1 to 5 minutes. Drying may be performed under reduced pressure or normal pressure.
  • a step of exposing the photosensitive resin composition layer with actinic rays through a predetermined photomask examples include visible rays, ultraviolet rays, far infrared rays, charged particle beams, X-rays, and laser beams.
  • the light source examples include sunlight, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a semiconductor laser.
  • the exposure dose is not particularly limited, but is preferably 20 to 300 mJ / cm 2 , and more preferably 20 to 100 mJ / cm 2 from the viewpoint of production cost.
  • a component having a (meth) acryloyl group in the photosensitive resin composition reacts to undergo photocuring reaction.
  • an alkaline aqueous solution is usually used as the developer.
  • the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; aqueous solutions of carbonates such as sodium carbonate, potassium carbonate and sodium hydrogencarbonate; hydroxytetramethylammonium and hydroxytetraethylammonium.
  • an aqueous solution of an organic alkali is usually used as the developer.
  • a surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be added and used.
  • a developing method there are a dip method and a shower method, but the shower method is preferable.
  • the temperature of the developer is preferably 20 to 45 ° C.
  • the development time is appropriately determined according to the film thickness and the solubility of the photosensitive resin composition.
  • Post-heating (post-baking) step The post-baking temperature is preferably 50 to 280 ° C., more preferably 100 to 250 ° C.
  • the post-bake time is preferably 5 minutes to 2 hours.
  • Production Example 1 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 60 parts of styrene, 20 parts of methyl methacrylate, 20 parts of methacrylic acid, and 217 parts of diethylene glycol dimethyl ether. After replacing the gas phase in the system with nitrogen, 36 parts of a solution of 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 30 parts of diethylene glycol dimethyl ether was added and heated to 90 ° C. The mixture was further reacted at the same temperature for 4 hours.
  • hydrophilic vinyl resin (A-1).
  • the acid value in terms of solid content of the hydrophilic vinyl resin was 131.5.
  • Mn by GPC was 4,000.
  • the hydrophilic vinyl resin had an SP value of 10.8 and an HLB value of 7.1.
  • Production Example 2 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen introduction tube was charged with 90 parts of styrene, 10 parts of methyl methacrylate, 30 parts of methacrylic acid, and 327 parts of propylene glycol monomethyl ether acetate. After replacing the gas phase part in the system with nitrogen, 38 parts of a solution in which 8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 30 parts of propylene glycol monomethyl ether acetate were added, And further reacted at the same temperature for 4 hours.
  • hydrophilic vinyl resin (A-2).
  • the acid value in terms of solid content of the hydrophilic vinyl resin was 96.1.
  • Mn by GPC was 4,500.
  • the hydrophilic vinyl resin had an SP value of 11.1 and an HLB value of 6.8.
  • the reaction product was further charged with 91 parts of tetrahydrophthalic anhydride, further reacted at 90 ° C. for 5 hours, and then diluted with propylene glycol monomethyl ether acetate so that the content of hydrophilic epoxy resin was 60%.
  • a 60% propylene glycol monomethyl ether acetate solution of epoxy resin (A-3) was obtained.
  • the acid value in terms of solid content of the hydrophilic epoxy resin was 88.4.
  • the Mn by GPC was 2,200.
  • the hydrophilic epoxy resin had an SP value of 11.3 and an HLB value of 9.8.
  • Examples 1 to 9 and Comparative Examples 1 to 4 According to the number of parts in Table 1, a solution of the hydrophilic resin (A-1) produced in Production Example 1 in a glass container, the following (B-1), (C-1), (C-3), ( D-1), (D-2) surfactants (G-1) and (G-2), and acrylic-modified alkoxypolysiloxane (E-1) produced in Production Example 4 were charged until uniform. The mixture was stirred to obtain a photosensitive resin composition of Example 1. Further, using the same apparatus, the photosensitive resin compositions of Examples 2 to 9 and Comparative Examples 1 to 4 were obtained in the same manner using the raw materials in the number of parts shown in Table 1.
  • the number average molecular weight (Mn) of the compound (E) was measured using HLC-8320GPC (manufactured by Tosoh Corp.) and THF solvent, TSK standard polystyrene (Tosoh Corp.) as a reference substance.
  • GPC workstation EcoSEC-WS manufactured by Tosoh Corporation was used as analysis software.
  • a photosensitive resin composition was applied onto a 10 cm ⁇ 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 ⁇ m. This coating film was heated on a hot plate at 80 ° C. for 3 minutes, and then developed with a 0.05% aqueous KOH solution for 30 seconds to evaluate the developability.
  • the evaluation criteria are as follows. A: There is no residue visually. ⁇ : There is a slight residue visually. ⁇ : There are many residues by visual inspection. X: Development is not possible.
  • a photosensitive resin composition was applied onto a 10 cm ⁇ 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 ⁇ m.
  • This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
  • the resulting coating film was irradiated with 60 mJ / cm 2 of light from an ultrahigh pressure mercury lamp through a mask for forming a photospacer (illuminance 22 mW / cm 2 in terms of i-line).
  • a photospacer luminance 22 mW / cm 2 in terms of i-line.
  • alkali development was performed using a 0.05% aqueous KOH solution.
  • post-baking was performed at 230 ° C. for 30 minutes to form a photo spacer on the glass substrate.
  • the elastic recovery characteristic of the photospacer can be evaluated by the “elastic recovery rate” when a certain pressure defined by the following formula (1) is applied.
  • the elastic recovery characteristic was evaluated by measuring the elastic recovery rate under a pressure condition of 0.5 mN / ⁇ m 2 .
  • a micro hardness tester Fischer Instruments, Inc .; “Fischer Scope H-100”
  • a planar indenter with a square cross section for one photo spacer selected arbitrarily from among photo spacers formed on a glass substrate 50 ⁇ m ⁇ 50 ⁇ m
  • a load was applied to 0.5 mN / ⁇ m 2 over 30 seconds at a load speed of 0.017 mN / ⁇ m 2 ⁇ sec and held for 5 seconds.
  • the amount of deformation from the initial position of the photospacer in a state where a load was applied was measured.
  • the amount of change at this time is defined as a total deformation amount T 0 ( ⁇ m).
  • T 0 The deformation amount from the initial position of the photo spacer at this time.
  • T 1 The deformation amount from the initial position of the photo spacer at this time.
  • a photosensitive resin composition was applied onto a 10 cm ⁇ 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 ⁇ m.
  • This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
  • the resulting coating film was irradiated with 60 mJ / cm 2 of light from an ultrahigh pressure mercury lamp through a mask for forming a photospacer (illuminance 22 mW / cm 2 in terms of i-line).
  • a photospacer luminance 22 mW / cm 2 in terms of i-line.
  • interval exposure gap
  • the photosensitive resin composition was applied onto a transparent glass substrate (thickness 0.7 mm) with a spin coater and dried to form a coating film.
  • This coating film was heated at 80 ° C. for 3 minutes.
  • the obtained coating film was irradiated with light from an ultrahigh pressure mercury lamp at 60 mJ / cm 2 (illuminance 22 mW / cm 2 in terms of i-line). Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a protective film having a thickness of 2 ⁇ m.
  • the transmittance of light having a wavelength of 400 nm was measured for the protective film obtained as described above using an ultraviolet-visible spectrophotometer UV-2400 (manufactured by Shimadzu Corporation).
  • the transmittance at 400 nm is shown in Table 1. When this value is 97% or more, it can be said that the transparency of the protective film is good.
  • the photosensitive resin compositions of the present invention of Examples 1 to 9 are excellent in all points of developability, elastic recovery characteristics, resolution, development adhesion, transparency, adhesion, and pencil hardness as shown in Table 1. Yes. On the other hand, since Comparative Examples 1 and 2 do not contain the solvent (D), the developability is poor. Since Comparative Examples 3 and 4 do not contain the hydrophilic resin (A), development cannot be performed.
  • the photosensitive resin composition of the present invention is excellent in developability and elastic recovery characteristics after curing and adhesion to a glass substrate, a photo spacer for a display element, a protective film for a color filter, a protective film for a touch panel, or an insulating film for a touch panel Can be suitably used. Furthermore, it is also suitable as a photosensitive resin composition for various other resist materials such as a photo solder resist, a photosensitive resist film, a photosensitive resin relief plate, a screen plate, a photoadhesive or a hard coat material.

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Abstract

La présente invention a pour objet une composition de résine photosensible qui a une grande aptitude au développement, qui procure un produit durci présentant d'excellentes caractéristiques de récupération de module d'élasticité et adhérence, et qui permet la formation d'un espaceur très fin. Une composition de résine photosensible d'après la présente invention est caractérisée en ce qu'elle contient (A) une résine hydrophile, (B) un (méth)acrylate polyfonctionnel, (C) un initiateur de photopolymérisation, (D) un solvant contenant un HLB se situant dans la plage de 8,0 à 30,0 (limites comprises) et (E) un composé qui est un produit de condensation qui contient, en qualité de monomère composant principal, un composé représenté par la formule générale (1). (Dans la formule (1), R1 représente un ou plusieurs groupes organiques qui sont sélectionnés dans le groupe constitué d'un groupe (méth)acryloyloxyalkylique, d'un groupe glycidoxyalkyle, d'un groupe mercaptoalkyle et d'un groupe aminoalkyle, chacun d'eux contenant un groupe alkyle comportant de 1 à 6 atomes de carbone ; R2 représente un groupe hydrocarbure aliphatique saturé comportant de 1 à 12 atomes de carbone ou un groupe hydrocarbure aromatique comportant de 6 à 12 atomes de carbone ; R3 représente un groupe alkyle comportant de 1 à 4 atomes de carbone ; M représente un ou plusieurs atomes sélectionnés dans le groupe constitué d'un atome de silicium, d'un atome de titane et d'un atome de zirconium ; et m représente 0 ou 1.)
PCT/JP2014/063779 2013-05-30 2014-05-26 Composition de résine photosensible, photoespaceur, film protecteur pour filtres colorés et film protecteur ou film isolant d'écran tactile WO2014192671A1 (fr)

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JP2015519839A JP6377056B2 (ja) 2013-05-30 2014-05-26 感光性樹脂組成物、フォトスペーサー、カラーフィルター用保護膜、及び、タッチパネルの保護膜もしくは絶縁膜
CN201480026139.1A CN105190440B (zh) 2013-05-30 2014-05-26 感光性树脂组合物、光学间隔件、彩色滤色器用保护膜和触摸面板的保护膜或绝缘膜
KR1020157032058A KR102326631B1 (ko) 2013-05-30 2014-05-26 감광성 수지 조성물, 포토스페이서, 컬러 필터용 보호막, 및, 터치 패널의 보호막 혹은 절연막

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016186609A (ja) * 2015-03-27 2016-10-27 三洋化成工業株式会社 感光性樹脂組成物
EP3330338A1 (fr) * 2016-12-05 2018-06-06 Henkel AG & Co. KGaA Composition adhésive liquide, feuille adhésive et procédé de liaison adhésive
EP3460828A4 (fr) * 2016-05-18 2019-05-22 Soken Chemical & Engineering Co., Ltd. Composition de résine photodurcissable, couche de résine de celle-ci, et moule pour empreinte

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018151628A (ja) * 2017-03-10 2018-09-27 日本化薬株式会社 感光性樹脂組成物、その硬化物及び物品
CN110032041B (zh) * 2019-05-07 2020-11-10 深圳市华星光电半导体显示技术有限公司 光阻组合物、显示面板及其制备方法
US10996518B1 (en) 2019-12-26 2021-05-04 Industrial Technology Research Institute Light switchable device
CN111458977A (zh) * 2020-04-15 2020-07-28 Tcl华星光电技术有限公司 一种光刻胶及其制备的显示面板
US11300875B2 (en) 2020-04-15 2022-04-12 Tcl China Star Optoelectronics Technology Co., Ltd. Photoresist, display panel and display device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007047247A (ja) * 2005-08-08 2007-02-22 Toray Ind Inc 感光性ペースト組成物およびそれを用いたフィールドエミッションディスプレイ部材
JP2007226115A (ja) * 2006-02-27 2007-09-06 Fujifilm Corp 感光性組成物及び感光性フィルム、並びに永久パターン形成方法
JP2010006982A (ja) * 2008-06-27 2010-01-14 Asahi Kasei E-Materials Corp 感光性ポリオルガノシロキサン組成物、ポリオルガノシロキサン硬化レリーフパターン及びその形成方法、並びに半導体装置及びその製造方法
JP2010229382A (ja) * 2009-02-19 2010-10-14 Sanei Kagaku Kk Ｓｉ系樹脂配合硬化性樹脂組成物
JP2012215837A (ja) * 2011-03-31 2012-11-08 Jsr Corp 感放射線性組成物、並びに硬化膜及びその形成方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3859182B2 (ja) 1997-03-27 2006-12-20 東京応化工業株式会社 ネガ型ホトレジスト組成物
JP4839525B2 (ja) 2000-09-29 2011-12-21 大日本印刷株式会社 感光性樹脂組成物および液晶ディスプレイ用カラーフィルタ
JP4837315B2 (ja) 2005-06-29 2011-12-14 凸版印刷株式会社 フォトスペーサ用感光性樹脂組成物及びそれを用いた液晶表示装置用カラーフィルタ
TWI396941B (zh) * 2006-02-22 2013-05-21 Sanyo Chemical Ind Ltd 感光性樹脂組合物
KR101320243B1 (ko) * 2010-12-28 2013-10-23 롬엔드하스전자재료코리아유한회사 감광성 수지 조성물, 이를 이용한 보호막 및 전자부품
CN103348289B (zh) * 2011-03-22 2016-04-13 Jsr株式会社 感放射线性组成物以及硬化膜及其形成方法
JP5981167B2 (ja) * 2011-03-24 2016-08-31 東京応化工業株式会社 感光性樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007047247A (ja) * 2005-08-08 2007-02-22 Toray Ind Inc 感光性ペースト組成物およびそれを用いたフィールドエミッションディスプレイ部材
JP2007226115A (ja) * 2006-02-27 2007-09-06 Fujifilm Corp 感光性組成物及び感光性フィルム、並びに永久パターン形成方法
JP2010006982A (ja) * 2008-06-27 2010-01-14 Asahi Kasei E-Materials Corp 感光性ポリオルガノシロキサン組成物、ポリオルガノシロキサン硬化レリーフパターン及びその形成方法、並びに半導体装置及びその製造方法
JP2010229382A (ja) * 2009-02-19 2010-10-14 Sanei Kagaku Kk Ｓｉ系樹脂配合硬化性樹脂組成物
JP2012215837A (ja) * 2011-03-31 2012-11-08 Jsr Corp 感放射線性組成物、並びに硬化膜及びその形成方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016186609A (ja) * 2015-03-27 2016-10-27 三洋化成工業株式会社 感光性樹脂組成物
EP3460828A4 (fr) * 2016-05-18 2019-05-22 Soken Chemical & Engineering Co., Ltd. Composition de résine photodurcissable, couche de résine de celle-ci, et moule pour empreinte
EP3330338A1 (fr) * 2016-12-05 2018-06-06 Henkel AG & Co. KGaA Composition adhésive liquide, feuille adhésive et procédé de liaison adhésive
WO2018104074A1 (fr) * 2016-12-05 2018-06-14 Henkel Ag & Co. Kgaa Composition adhésive liquide, feuille adhésive et procédé de fixation par collage
CN110023445A (zh) * 2016-12-05 2019-07-16 汉高股份有限及两合公司 液体粘合剂组合物、粘合剂片材和粘合剂粘合方法
CN110023445B (zh) * 2016-12-05 2021-09-14 汉高股份有限及两合公司 液体粘合剂组合物、粘合剂片材和粘合剂粘合方法
US11193050B2 (en) 2016-12-05 2021-12-07 Henkel Ag & Co. Kgaa Liquid adhesive composition, adhesive sheet, and adhesive bonding method

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CN105190440B (zh) 2019-08-06
TWI613514B (zh) 2018-02-01
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