WO2014038576A1 - Composition de résine photosensible pour entretoise photo et entretoise photo - Google Patents

Composition de résine photosensible pour entretoise photo et entretoise photo Download PDF

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Publication number
WO2014038576A1
WO2014038576A1 PCT/JP2013/073765 JP2013073765W WO2014038576A1 WO 2014038576 A1 WO2014038576 A1 WO 2014038576A1 JP 2013073765 W JP2013073765 W JP 2013073765W WO 2014038576 A1 WO2014038576 A1 WO 2014038576A1
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Prior art keywords
photospacer
group
photosensitive resin
repeating unit
resin composition
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PCT/JP2013/073765
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English (en)
Japanese (ja)
Inventor
田中　晋介
加原　浩二
悠太 湊邉
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株式会社日本触媒
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Priority claimed from JP2012284668A external-priority patent/JP6184094B2/ja
Application filed by 株式会社日本触媒 filed Critical 株式会社日本触媒
Priority to CN201380046137.4A priority Critical patent/CN104641295B/zh
Priority to KR1020157005861A priority patent/KR102149152B1/ko
Publication of WO2014038576A1 publication Critical patent/WO2014038576A1/fr

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    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
    • 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
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • 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 for a photospacer and a photospacer.
  • a liquid crystal layer is formed between a pair of substrates, and a spacer is disposed in order to keep the distance between the substrates constant.
  • columnar spacers photo spacers
  • the photospacer is formed by applying a photosensitive resin composition on a substrate, exposing it to a predetermined mask, and then developing it. Since the photo spacer can be formed at an arbitrary position, for example, it can be formed only on the black matrix to prevent the display characteristics from deteriorating due to the spacer.
  • the characteristics required for the photospacer include high elastic recovery for maintaining a constant substrate spacing, fracture strength, adhesion to the substrate, and the like. Moreover, the photosensitive resin composition for photospacers is required to have a small amount of development residue. These characteristics are required to be satisfied at a higher level as the quality of liquid crystal display devices increases. Furthermore, there is a demand for a photospacer that sufficiently satisfies the above characteristics even in the case of a thin columnar shape.
  • the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to form a photo spacer that has excellent substrate adhesion, high elastic recovery rate and high breaking strength, and development.
  • the object is to provide a photosensitive resin composition for a photospacer with little residue.
  • the photosensitive resin composition for a photospacer of the present invention contains, as a binder polymer, an acrylic resin having a repeating unit having a ring structure in the main chain and a repeating unit having two or more oxyalkylene groups in the side chain.
  • the photosensitive resin composition for a photospacer of the present invention includes a polyfunctional monomer, a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, and a maximum at a wavelength of 230 nm to 290 nm. And a second photopolymerization initiator having an absorption wavelength.
  • the repeating unit having a ring structure in the main chain is at least one selected from repeating units represented by the general formulas (1) to (7).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or a linear or branched group having 1 to 30 carbon atoms It is an alkyl group.
  • the repeating unit which has a 2 or more oxyalkylene group in the said side chain is a repeating unit represented by General formula (10).
  • R 7 , R 8 and R 9 are each independently a hydrogen atom or a methyl group
  • R 10 is a linear or branched alkyl group having 1 to 20 carbon atoms, carbon A straight-chain or branched alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • AO is an oxyalkylene group having 2 to 20 carbon atoms
  • x is 0
  • y represents 0 or 1
  • n is 2 or more.
  • the acrylic resin further includes a repeating unit having an acid group in the side chain.
  • the acrylic resin further has a repeating unit having a carbon double bond in the side chain.
  • a binder polymer for a photospacer is provided.
  • This binder polymer for photospacers is an acrylic resin having a repeating unit having a ring structure in the main chain and a repeating unit having two or more oxyalkylene groups in the side chain.
  • the repeating unit which has a 2 or more oxyalkylene group in the said side chain is a repeating unit represented by General formula (10).
  • a photospacer is provided. This photospacer is formed by the photosensitive resin composition for photospacers.
  • a liquid crystal display is provided. This liquid crystal display includes the photo spacer.
  • a resin composition can be provided.
  • the photosensitive resin composition for a photospacer of the present invention can form a non-reverse tapered photospacer by further including two or more photopolymerization initiators having different maximum absorption wavelengths.
  • the non-reversely tapered photospacer formed from the photosensitive resin composition for photospacers is remarkably excellent in substrate adhesion, elastic recovery rate and breaking strength. Further, the photospacer can prevent bubbles from being mixed into the liquid crystal layer, and can contribute to the improvement of the display performance of the display device.
  • (A) And (b) is a schematic sectional drawing of the photospacer formed with the photosensitive resin composition of this invention. It is a schematic sectional drawing explaining the photo spacer of a reverse taper shape.
  • the photospacer photosensitive resin composition of the present invention is a binder polymer having a repeating unit (A) having a ring structure in the main chain and two or more oxyalkylene groups in the side chain.
  • An acrylic resin having a unit (B) is included.
  • Such a binder polymer can be used for various cured products that require breaking strength, and when the binder polymer is used for a photospacer, a photospacer having a high elastic modulus can be obtained.
  • the photosensitive resin composition for a photospacer of the present invention may further contain a polyfunctional monomer, a photopolymerization initiator, a solvent, and an additive.
  • An acrylic resin (binder polymer) having a repeating unit (A) having a ring structure in the binder polymer main chain and a repeating unit (B) having two or more oxyalkylene groups in the side chain is a monomer having a ring structure in the main chain It can be obtained by polymerizing a monomer composition comprising (a) and a monomer (b) having two or more oxyalkylene groups in the side chain.
  • the monomer composition may further include a monomer (c) constituting the repeating unit (C) having an acid group in the side chain and / or another monomer (e) constituting another repeating unit (E).
  • Examples of the repeating unit (A) having a ring structure in the main chain include a repeating unit having a maleimide structure, an N-substituted maleimide structure, a lactone ring structure, a glutaric anhydride structure, a maleic anhydride structure, and the like. Of these, a maleimide structure or an N-substituted maleimide structure is preferable.
  • an acrylic resin having a repeating unit having a maleimide structure or an N-substituted maleimide structure in the main chain a photosensitive resin composition for a photospacer having higher solubility in a developer can be obtained.
  • the repeating unit (A) having a ring structure in the main chain is preferably at least one selected from repeating units represented by the general formulas (1) to (3). It is more preferable that it is a repeating unit represented by. If an acrylic resin having a repeating unit represented by the general formula (1) is used, a curable resin composition capable of forming a cured product with higher breaking strength can be obtained, and particularly preferably, a more breaking strength is obtained.
  • the photosensitive resin composition for photospacers which can form a high photospacer can be obtained.
  • the repeating unit (A) having a ring structure in the main chain may be at least one selected from repeating units represented by the general formulas (4) to (7).
  • the repeating unit represented by the general formula (4) or (7) is preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or a linear or branched group having 1 to 30 carbon atoms
  • An alkyl group preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Group, more preferably a methyl group.
  • the repeating unit (A) having a ring structure in the main chain is composed of the monomer (a) having a ring structure in the main chain.
  • the monomer (a) having a ring structure in the main chain include maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide.
  • N-o-chlorophenylmaleimide Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o- Aromatic substituted maleimides such as methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide, isopropyl Alkyl-substituted maleimides such as Rumareimido like.
  • maleimide, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are preferable, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are more preferable, and benzylmaleimide is more preferable.
  • Examples of the monomer (a) constituting the repeating unit represented by the general formulas (4) to (7) include 1,6-dienes represented by the general formula (8) or (9). In formulas (8) and (9), R 1 , R 2 and R 3 are as described above.
  • the content ratio of the monomer (a) constituting the repeating unit (A) having a cyclic structure in the main chain is such that the monomer (a), the monomer (b), the monomer (c) in the monomer composition and
  • the amount is preferably 5% by weight to 50% by weight, more preferably 8% by weight to 30% by weight, and still more preferably 10% by weight to 20% by weight, based on the total amount of the monomer (e).
  • the acrylic resin as the binder polymer has the repeating unit (A) having a ring structure in the main chain
  • a photosensitive resin composition for a photospacer having high solubility in a developer can be obtained. If such a photosensitive resin composition for photospacers is used, a photospacer can be formed without producing a development residue.
  • the acrylic resin which has a repeating unit (A) which has a cyclic structure in a principal chain is used, the photosensitive resin composition for photo spacers which can form the photo spacer excellent in board
  • Examples of the repeating unit (B) having two or more oxyalkylene groups in the side chain include a repeating unit represented by the general formula (10).
  • R 7 , R 8 and R 9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • R 10 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. And preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms still more preferably a linear alkyl group having 1 to 5 carbon atoms
  • a phenyl group or a biphenyl group particularly preferably a methyl group, a phenyl group or a biphenyl group.
  • the alkyl group, the alkenyl group, and the aromatic hydrocarbon group may have a substituent.
  • AO represents an oxyalkylene group.
  • the oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2.
  • the repeating unit (B) may contain one or more oxyalkylene groups.
  • x represents an integer of 0-2.
  • y represents 0 or 1;
  • n represents an average addition mole number of the oxyalkylene group and is 2 or more, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 15.
  • the repeating unit (B) having two or more oxyalkylene groups in the side chain is composed of a monomer (b) having two or more oxyalkylene groups in the side chain.
  • a monomer (b) the monomer represented by General formula (11) is mentioned, for example.
  • R 7 , R 8 , R 9 , R 10 , AO, x, y and n are as described above.
  • the monomer represented by the general formula (11) examples include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO 4 mol), Methoxypolyethylene glycol (meth) acrylate (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethylhexyl Diethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxy polypropylene glycol Le (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate (EO4-17 moles), nonylphenoxy polypropyl
  • the content ratio of the monomer (b) constituting the repeating unit (B) having two or more oxyalkylene groups in the side chain is the monomer (a), monomer (b), monomer in the monomer composition.
  • it is 0.5 wt% to 55 wt%, more preferably 1 wt% to 50 wt%, and even more preferably 1 wt% to 45 wt%, based on the total amount of (c) and monomer (e). %.
  • the above-mentioned acrylic resin has a repeating unit (B) having two or more oxyalkylene groups in the side chain, thereby forming a photospacer having a high crosslink density, a high elastic recovery rate and a high breaking strength.
  • Resin composition can be obtained.
  • a photosensitive resin composition for a photospacer is constituted by combining such an acrylic resin and a polyfunctional monomer described below (preferably a polyfunctional monomer having no oxyalkylene group), the above effect is particularly effective. Become prominent.
  • the acrylic resin has a repeating unit (C) having an acid group in the side chain. If acrylic resin has the repeating unit (C) which has an acid group in a side chain, the photosensitive resin composition for photospacers which is excellent in alkali developability can be obtained.
  • the monomer (c) constituting the repeating unit (C) having an acid group in the side chain include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, itaconic acid, ⁇ -carboxy-poly Monomers having a carboxyl group such as caprolactone monoacrylate; monomers having a carboxylic anhydride group such as maleic anhydride and itaconic anhydride. Of these, (meth) acrylic acid is preferred.
  • the content ratio of the monomer (c) constituting the repeating unit (C) having an acid group in the side chain is the monomer (a), the monomer (b), the monomer (c) and the monomer composition in the monomer composition.
  • the amount is preferably 10% by weight to 90% by weight, more preferably 15% by weight to 85% by weight, and still more preferably 20% by weight to 80% by weight with respect to the total amount of the monomer (e).
  • the acrylic resin has a repeating unit (D) having a carbon double bond in the side chain. If the acrylic resin has a repeating unit (D) having a carbon double bond in the side chain, photosensitivity for photospacer that can form a photospacer with high exposure sensitivity and high elastic recovery and breaking strength. Resin composition can be obtained.
  • the repeating unit (D) having a carbon double bond in the side chain has two or more (preferably, part) acid groups of the repeating unit (C) having an acid group in the side chain as a reaction point. It can be obtained by adding a compound having a heavy bond.
  • the acid group of the repeating unit (C) having an acid group in the side chain is a carboxyl group
  • a compound having an epoxy group and a double bond, an isocyanate group and a double bond are used as the compound having a carbon double bond.
  • the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl.
  • Examples thereof include benzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether.
  • Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate.
  • the acid group of the repeating unit (C) having an acid group in the side chain is a carboxylic anhydride group
  • a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond.
  • Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.
  • the acrylic resin may further have another repeating unit (E) derived from another monomer (e) copolymerizable with the monomer (a), monomer (b) and / or monomer (c).
  • Examples of other monomers (e) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • (Meth) acrylic acid amides aromatic vinyl compounds such as styrene, vinyl toluene and ⁇ -methyl styrene, butadiene or substituted butadiene compounds such as butadiene and isoprene, ethylene, propylene, vinyl chloride, acrylonitrile, etc. Ethylene or substituted ethylene compounds; vinyl esters such as vinyl acetate and the like. These monomers may be used alone or in combination of two or more.
  • the content ratio of the monomer (e) constituting the other repeating unit (E) in the monomer composition is such that the monomer (a), monomer (b), monomer (c) and monomer (e) in the monomer composition are
  • the total amount is preferably 0% to 55% by weight, more preferably 5% to 50% by weight, and still more preferably 10% to 45% by weight.
  • the acrylic resin may be a random copolymer or a block copolymer.
  • the acrylic resin preferably has a weight average molecular weight of 3,000 to 200,000, more preferably a value measured by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent. It is 4,000 to 100,000, and more preferably 5,000 to 50,000. If it is such a range, the photosensitive resin composition for photospacers which ensures heat resistance and has a viscosity suitable for film formation can be obtained.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • the acid value of the acrylic resin is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 25 mgKOH / g to 200 mgKOH / g, and further preferably 30 mgKOH / g to 150 mgKOH / g. If it is such a range, the photosensitive resin composition for photospacers which can form the photospacer which is excellent in alkali developability, has little generation
  • the acrylic resin can be obtained by polymerizing the monomer (a) and the monomer (b) and, if necessary, the monomer composition containing the monomer (c) and / or (e) by any appropriate method. it can.
  • the polymerization method include a solution polymerization method.
  • the monomer composition may contain any appropriate solvent.
  • the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl.
  • ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether
  • ketones such as acetone and methyl ethyl ketone
  • esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbon
  • the polymerization concentration when polymerizing the monomer composition is preferably 5% by weight to 90% by weight, more preferably 5% by weight to 50% by weight, and still more preferably 10% by weight to 50% by weight. .
  • the monomer composition may contain any appropriate polymerization initiator.
  • the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-amyl peroxy-2.
  • Organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate).
  • the content of the polymerization initiator is preferably 0.1 parts by weight to 15 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the total monomers in the monomer composition.
  • the polymerization temperature when polymerizing the acrylic resin by the solution polymerization method is preferably 40 ° C. to 150 ° C., more preferably 60 ° C. to 130 ° C.
  • the compound which has the said carbon double bond is added to the obtained acrylic resin after the said superposition
  • Any appropriate method can be adopted as a method for adding a compound having a carbon double bond.
  • a compound having a carbon double bond is reacted with part or all (preferably part) of the acid group of the repeating unit (C) having an acid group in the side chain.
  • the repeating unit (D) having a carbon double bond in the side chain can be formed.
  • the addition amount of the compound having a carbon double bond is preferably 5% with respect to 100 parts by weight of the acrylic resin after the polymerization (that is, the acrylic resin before adding the compound having a carbon double bond). Part or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. If it is such a range, the photosensitive resin composition for photo spacers which is excellent in exposure sensitivity can be obtained. By using such a photosensitive resin composition for a photospacer, a dense cured coating film can be formed, and a photospacer having excellent substrate adhesion, high elastic recovery rate and high breaking strength can be formed.
  • the photosensitive resin for photospacer has a sufficient hydroxyl group generated by the addition of the compound having a carbon double bond and is excellent in solubility in an alkaline developer.
  • a composition can be obtained.
  • the upper limit of the amount of the compound having a carbon double bond is preferably 100 parts by weight with respect to 100 parts by weight of the acrylic resin after polymerization (that is, the acrylic resin before adding the compound having a carbon double bond). It is 170 parts by weight or less, more preferably 150 parts by weight or less, and still more preferably 140 parts by weight or less.
  • polymerization inhibitor examples include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol.
  • catalyst examples include tertiary amines such as dimethylbenzylamine and triethylamine.
  • the photosensitive resin composition for a photospacer of the present invention may further contain a polyfunctional monomer.
  • the polyfunctional monomer include polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol di
  • dipentaerythritol tetra (meth) acrylate dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tris (hydroxy) isocyanurate tri (meth) acrylate and the like are preferred.
  • these polyfunctional monomers are used, a photo spacer having a high crosslinking density can be obtained because of the large number of functional groups.
  • a binder polymer having an oxyalkylene group is used.
  • the polyfunctional monomer may or may not have an oxyalkylene group.
  • a polyfunctional monomer having no oxyalkylene group is used.
  • the content ratio of the polyfunctional monomer is preferably 10 parts by weight to 90 parts by weight, and more preferably 30 parts by weight with respect to 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer. Is 85 parts by weight, and more preferably 50 parts by weight to 85 parts by weight.
  • the photosensitive resin composition for a photospacer of the present invention may contain any appropriate photopolymerization initiator.
  • the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ket
  • the content of the photopolymerization initiator is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer. Is 0.5 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, and most preferably 1.5 to 30 parts by weight. 5 parts by weight.
  • the photosensitive resin composition for a photospacer of the present invention includes two or more photopolymerization initiators having maximum absorption wavelengths in different wavelength ranges.
  • the photosensitive resin composition for a photospacer of the present invention includes a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm and a second photopolymerization start having a maximum absorption wavelength at a wavelength of 230 nm to 290 nm. Agent.
  • ultraviolet light can be efficiently used during exposure.
  • a photospacer having a shape having substantially no diameter difference in the height direction or a shape having a narrower upper part than the lower part is formed.
  • the photo spacer having such a shape has excellent substrate adhesion, and has a high elastic recovery rate and high breaking strength. Further, the photospacer can prevent bubbles from being mixed into the liquid crystal layer, and can contribute to the improvement of the display performance of the display device.
  • a shape having substantially no diameter difference in the height direction and a shape whose upper part is narrower than the lower part are collectively referred to as “non-reverse tapered shape”.
  • the first photopolymerization initiator preferably has a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, more preferably has a maximum absorption wavelength at a wavelength of 295 nm to 350 nm, and more preferably has a maximum absorption wavelength of 295 nm to 340 nm.
  • a photopolymerization initiator having a maximum absorption wavelength on the wavelength side higher than 380 nm is used, it is difficult to control the thickness of the photo spacer, and a photo spacer that is too thick may be formed.
  • the “maximum absorption wavelength” refers to the wavelength of maximum absorption at which the absorbance measured at an optical path length of 1 cm is 0.5 or more for a photopolymerization initiator solution having a concentration of 0.001% by weight.
  • an ⁇ -aminoketone compound is preferably used, and more preferably an ⁇ -aminoketone compound represented by the general formula (12) is used.
  • an ⁇ -aminoketone compound represented by the general formula (12) is used.
  • X 1 and X 2 are each independently a methyl group, an ethyl group, a benzyl group or a 4-methylbenzyl group, preferably a methyl group.
  • NX 3 X 4 is a dimethylamino group, a diethylamino group or a morpholino group, preferably a dimethylamino group or a morpholino group, more preferably a morpholino group.
  • X 5 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group, or a morpholino group, preferably carbon It is an alkylthio group or morpholino group having 1 to 8 carbon atoms, more preferably an alkylthio group or morpholino group having 1 to 3 carbon atoms, and further preferably a methylthio group.
  • ⁇ -aminoketone compound examples include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, and 2-methyl.
  • 2-morpholino-1-phenylpropan-1-one 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one
  • 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one 1- (4-butylphenyl) -2-dimethylamino-2-methyl Propan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl 1- (4-methylthiophenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl
  • first photopolymerization initiator Commercially available products may be used as the first photopolymerization initiator.
  • first photopolymerization initiator examples include trade names “Irgacure 907”, “Irgacure 369”, and “Irgacure 379” manufactured by BASF Japan.
  • the content ratio of the first photopolymerization initiator is preferably 0.1 parts by weight to 30 parts by weight with respect to 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer.
  • the amount is preferably 0.5 to 10 parts by weight, and more preferably 1.0 to 5 parts by weight.
  • the second photopolymerization initiator preferably has a maximum absorption wavelength at a wavelength of 230 nm to 290 nm, more preferably a maximum absorption wavelength at a wavelength of 240 nm to 280 nm, and still more preferably a maximum absorption wavelength at a wavelength of 250 nm to 270 nm.
  • an ⁇ -hydroxyketone compound is preferably used, more preferably an ⁇ -hydroxyketone compound represented by the general formula (13) or the general formula (14) is used. More preferably, an ⁇ -hydroxyketone compound represented by the general formula (14) is used. If such a compound is used, a photosensitive resin composition for a photospacer that can form a photospacer having a non-inverted taper shape and a small diameter can be obtained.
  • X 6 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or An alkoxy group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 2 carbon atoms.
  • X 7 and X 8 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.
  • X 7 and X 8 may be bonded to each other to form a cycloalkyl group having 4 to 8 carbon atoms (preferably 6 to 8, more preferably 6).
  • X 9 to X 12 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably methyl It is a group.
  • X 9 and X 10 and / or X 11 and X 12 may be bonded to form a cycloalkyl group having 4 to 8 carbon atoms.
  • the alkyl group, alkoxy group, alkyl group and cycloalkyl group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, and a halogen atom.
  • ⁇ -hydroxyketone compound examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenylbutan-1-one, 1- ( 4-methylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-octylphenyl) propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, -(4-methoxyphenyl) -2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methylpropan-1-one, 1- (4-chlorophenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4-bromophenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4-hydroxyphenyl)
  • a commercially available product may be used as the second photopolymerization initiator.
  • Examples of the commercially available second photopolymerization initiator include trade names “Irgacure 184”, “Irgacure 2959”, “Irgacure 127”, and “Darocure 1173” manufactured by BASF Japan.
  • the content ratio of the second photopolymerization initiator is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer. More preferably, it is 0.05 to 10 parts by weight, and still more preferably 0.07 to 1 part by weight.
  • the content ratio of the second photopolymerization initiator is preferably 5% by weight to 40% by weight with respect to the total weight of the first photopolymerization initiator and the second photopolymerization initiator. More preferably, it is 5 to 30% by weight, and further preferably 5 to 20% by weight. If it is such a range, the photosensitive resin composition for photospacers which can form a photospacer which is excellent in board
  • the total content ratio of the first photopolymerization initiator and the second photopolymerization initiator is preferably 0. 0 with respect to 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer.
  • the amount is 5 to 50 parts by weight, more preferably 1 to 10 parts by weight, and still more preferably 1.5 to 5 parts by weight.
  • a photopolymerization initiation assistant may be used in combination.
  • Photopolymerization initiation assistants can also be used in combination.
  • Specific examples of the photopolymerization initiation assistant include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa) Electric Works, Karenz MT (registered trademark) NR1), trimethylolpropane tris (trifunctional thiol compounds such as 3-mercaptopropionate; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) Butyrate) (made by Showa Denko KK, Karenz MT (registered trademark) PE1) and the like; and polyfunctional thiols such as difunctional thiol compounds such
  • the photosensitive resin composition for a photospacer of the present invention may contain any appropriate solvent.
  • the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy Esters such as butyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Chloroform, dimethyl sulfoxide, and the like Can be mentioned.
  • the amount of the solvent can be set
  • the photosensitive resin composition for a photospacer of the present invention may contain any appropriate additive as required.
  • additives for example, fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, Antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners, dispersants, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, zirconia, titanium), porous fine particles such as silica, Examples thereof include hollow fine particles such as silica.
  • the photosensitive resin composition for a photospacer of the present invention contains a UV absorber. If the photosensitive resin composition for photospacers containing a UV absorber is used, a photospacer having a small difference in diameter between the upper and lower sides can be obtained, and the photospacer can be formed into a thin column.
  • the photospacer formed by the photosensitive resin composition for a photospacer of the present invention is thin but has sufficient breaking strength.
  • the content of the UV absorber is based on 100 parts by weight of the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer.
  • the amount is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 3 parts by weight.
  • the photospacer of the present invention can be obtained using the above-mentioned photosensitive resin composition for photospacers. If the said photosensitive resin composition for photospacers is used, the photospacer which is excellent in board
  • the photospacer of the present invention can be suitably used as a spacer for a liquid crystal display, more specifically, a liquid crystal cell of a liquid crystal display.
  • the photo spacer can be formed by photolithography. Specifically, the photosensitive resin composition for photospacer is applied to a substrate and then dried. A photomask is placed on the obtained coating film to expose it, the coating film is cured, and then developed. Thus, a photo spacer can be formed. According to photolithography, a photo spacer can be formed at an arbitrary position. For example, in a liquid crystal display device, a photo spacer is formed only on a black matrix to prevent display characteristics from being deteriorated due to the spacer. can do.
  • Examples of the method for applying the photosensitive resin composition for photospacer include a method using a spin coater, bar coater, gravure coater, roll coater, knife coater, applicator and the like.
  • the drying temperature is preferably 40 ° C. to 200 ° C., more preferably 70 ° C. to 100 ° C.
  • the drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes.
  • the arrangement position of the photomask is arranged at any appropriate position according to the desired size of the photo spacer.
  • the photomask is disposed on the top of the coating film, and the distance between the coating film and the photomask is preferably 0 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 400 ⁇ m, still more preferably 20 ⁇ m to 300 ⁇ m, and particularly preferably 30 ⁇ m. ⁇ 200 ⁇ m.
  • the UV irradiation intensity (in terms of 365 nm illuminance) during the exposure is preferably 10 mJ / cm 2 to 200 mJ / cm 2 , more preferably 20 mJ / cm 2 to 150 mJ / cm 2 , and even more preferably 30 mJ / cm 2. ⁇ 100 mJ / cm 2 .
  • an alkaline aqueous solution is preferably used. This is because high-sensitivity development can be performed with less environmental burden.
  • the alkaline component for example, potassium hydroxide, sodium hydroxide, sodium carbonate or the like is used.
  • the alkali concentration of the aqueous alkali solution is preferably 0.01% to 5% by weight, more preferably 0.02% to 3% by weight, and further preferably 0.03% to 1% by weight. . If it is such a range, the said photosensitive resin composition for photospacers can be melt
  • a surfactant may be further added to the alkaline aqueous solution.
  • Post-baking may be performed after development.
  • the heating temperature during post-baking is preferably 150 ° C. to 300 ° C., more preferably 180 ° C. to 250 ° C.
  • the heating time is preferably 10 minutes to 90 minutes, more preferably 20 minutes to 60 minutes. Since the photosensitive resin composition for a photospacer of the present invention contains an acrylic resin having a repeating unit (B) having two or more oxyalkylene groups in the side chain, a photospacer having a high crosslinking density is formed by post-baking. can do.
  • Examples of the shape of the photospacer of the present invention include a columnar shape, a prismatic shape, a truncated cone shape, and a truncated pyramid shape.
  • the thickness of the lowermost part of the photospacer is preferably 3 ⁇ m 2 to 500 ⁇ m 2 , more preferably 15 ⁇ m 2 to 100 ⁇ m 2 in terms of the horizontal cross-sectional area of the photospacer.
  • the diameter at the bottom of the photospacer can be set to any appropriate range. Practically, it is preferably 2 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m, still more preferably 5 ⁇ m to 8.5 ⁇ m, and particularly preferably 5 ⁇ m to 8 ⁇ m.
  • the photo spacer which can respond to the high definition of a display apparatus can be obtained.
  • a photospacer having a diameter at the lowermost part of 5 ⁇ m to 8.5 ⁇ m (particularly preferably 5 ⁇ m to 8 ⁇ m) has a remarkable effect.
  • “diameter” means a length of a straight line that connects two points on the circumference of the lowermost surface and passes through the center of gravity of the lowermost surface. Therefore, when the photo spacer has a cylindrical shape or a truncated cone shape (that is, when the lowermost surface is circular), it means the diameter of the lowermost surface.
  • the height of the photo spacer can be set to any appropriate height depending on the desired substrate interval. The height of the photo spacer is, for example, 1 ⁇ m to 10 ⁇ m.
  • the photo spacer of the present invention preferably has a non-inverted taper shape.
  • 1 (a) and 1 (b) are schematic cross-sectional views of a non-reverse tapered photo spacer formed by the photosensitive resin composition for a photo spacer of the present invention.
  • FIG. 1A shows a photospacer 10 having substantially no diameter difference in the height direction.
  • FIG.1 (b) the photo spacer 20 whose upper part is thinner than the lower part is shown.
  • a shape that has substantially no difference in diameter in the height direction and a shape that is narrower in the upper part than the lower part are collectively referred to as a “non-inverted tapered shape”.
  • the “non-inverted taper shape” means that the horizontal cross-sectional area A1 of the portion H1 separated from the lower part of the photo spacer in the height direction (height L ⁇ 1/2 of the photo spacer) is A shape that is the same as or smaller than the horizontal cross-sectional area A2 of the portion H2 away from the bottom in the height direction (height L ⁇ 1/4 of the photo spacer).
  • the non-reverse taper-shaped photospacer is, for example, a photospacer photosensitive material containing two or more photopolymerization initiators having different maximum absorption wavelengths (for example, the first photopolymerization initiator and the second photopolymerization initiator). It can form using an adhesive resin composition.
  • the “reverse taper shape” refers to the shape shown in the schematic cross-sectional view of FIG. 2. Specifically, it is separated from the lower part of the photo spacer in the height direction (height L ⁇ 1/2 of the photo spacer).
  • the horizontal cross-sectional area of the portion H1 is larger than the horizontal cross-sectional area of the portion H2 that is separated from the lower part of the photo spacer in the height direction (height L ⁇ 1/4 of the photo spacer).
  • the ratio (A2 / A1) of the distant portion H2 to the horizontal sectional area A2 is preferably 1 to 1.3, more preferably 1 to 1.2, and still more preferably 1 to 1. 15, particularly preferably 1 to 1.1.
  • a photospacer having such a range of A2 / A1 has excellent substrate adhesion, and has a high elastic recovery rate and high fracture strength. Further, the photospacer can prevent bubbles from being mixed into the liquid crystal layer, and can contribute to the improvement of the display performance of the display device.
  • the compression ratio of the photo spacer of the present invention is 10% to 90%. A method for evaluating the compression rate will be described later.
  • the lower limit of the elastic recovery rate of the photospacer of the present invention is preferably 55% or more, more preferably 60% or more, still more preferably 65% or more, still more preferably 70% or more, and further preferably Is 75% or more, more preferably 80% or more, and particularly preferably 90% or more.
  • the upper limit of the elastic recovery rate of the photospacer of the present invention is, for example, 100%. The method for evaluating the elastic recovery rate will be described later.
  • the elastic recovery rate of the photospacer of the present invention is preferably 70% to 100%, more preferably 80%. ⁇ 95%.
  • the relationship between the elastic recovery rate b (%) of the photospacer of the present invention and the diameter a ( ⁇ m) at the lowermost part of the photospacer is preferably b> 3.1a + 45 in the range of the practical diameter a. More preferably, b> 3.1a + 50, and further preferably b> 3.1a + 53.
  • the lower limit of the breaking strength of the photospacer of the present invention is preferably 20 mN or more, more preferably 50 mN or more, further preferably 100 mN or more, further preferably 110 mN or more, and further preferably 120 mN or more. More preferably, it is 130 mN or more, More preferably, it is 145 mN or more, More preferably, it is 160 mN or more, Especially preferably, it is 175 mN or more, Most preferably, it is 190 mN or more. The higher the breaking strength, the better.
  • the upper limit value of the breaking strength of the photospacer of the present invention is, for example, preferably 300 mN. A method for evaluating the fracture strength will be described later.
  • the breaking strength of the photo spacer of the present invention is preferably 100 mN to 300 mN, more preferably 145 mN to 300 mN. Further, it is preferably 145 mN to 250 mN, more preferably 160 mN to 250 mN, still more preferably 175 mN to 210 mN, and particularly preferably 175 mN to 200 mN.
  • the load speed and unloading speed are both set to 4.7 mN / sec, the load up to 80 mN is loaded, the load is unloaded to 0.49 mN, and the load-deformation curve and unloading during loading A load-deformation curve was created.
  • the amount of deformation at a load of 80 mN at the time of loading was L1, and the compression rate was calculated by the following formula.
  • Compression rate (%) L1 ⁇ 100 / Spacer height (7)
  • Elastic recovery rate of photo spacer was measured using a micro compression tester (trade name: HM2000, manufactured by Fisher Instruments). It was measured.
  • the load speed and unloading speed are both set to 4.7 mN / sec, the load up to 80 mN is loaded, the load is unloaded to 0.49 mN, and the load-deformation curve and unloading during loading A load-deformation curve was created.
  • the amount of deformation at a load of 80 mN during loading was L1
  • the amount of deformation at a load of 0.49 mN during unloading was L2, and the elastic recovery rate was calculated by the following equation.
  • Elastic recovery rate (%) (L1-L2) ⁇ 100 / L1 (8) Fracture strength of the photo spacer
  • the break strength of the photo spacer was measured using a micro compression tester (trade name: HM2000, manufactured by Fisher Instruments). With a 100 ⁇ m square planar indenter, the load speed and the unloading speed were both set to 4.7 mN / sec, a load up to 300 mN was applied, and the load when the spacer was broken was read from the load-deformation curve.
  • Shape of photo spacer (non-reverse tapered shape / reverse tapered shape)
  • the evaluation of whether the shape of the photo spacer is a non-reverse tapered shape or a reverse tapered shape is performed using FE-SEM (trade name “S-4800”, manufactured by Hitachi, Ltd.).
  • L ⁇ 1/2) The diameter (diameter) D1 of the separated portion H1 and (the height L ⁇ 1/4) of the separated portion H2 are measured, and the diameter (diameter) D2 of the separated portion H2 is measured.
  • the horizontal sectional area A1 at H1, and the horizontal sectional area A2 at H2 were calculated. A case where A2 / A1 is 1 or more is a non-inverted taper shape.
  • PBO propylene glycol methyl ether acetate
  • PGMEA propylene glycol methyl ether acetate
  • nDM dodecyl mercaptan
  • 18 g of PGMEA and 8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank and mixed with stirring.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
  • the monomer composition and the chain transfer agent solution were added dropwise.
  • the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C.
  • PBO 0.5g was added 30 minutes after the completion of the dropping.
  • the temperature of the reaction vessel was raised to 115 ° C.
  • glycidyl methacrylate (GMA) in the reaction vessel 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzyl as a catalyst
  • Amine (DMBA) 0.5 g, PGMEA 16 g and PGME 6 g were charged and reacted at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-1) containing 39.4% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17200, and the acid value was 55 mgKOH / g.
  • the production conditions, solid content concentration, weight average molecular weight (Mw) and acid value of the copolymer solution are shown in Table 1 together with Production Examples 2 to 20.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-2) containing 39.3% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18000, and the acid value was 103 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-3) containing 39.0% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18200, and the acid value was 44 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-4) containing 39.5% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 25200, and the acid value was 56 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-5) containing 38.8% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 10400, and the acid value was 55 mgKOH / g.
  • the reaction vessel was charged with 42 g of PGMEA and 98 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-6) containing 39.6% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 19300, and the acid value was 54 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-8) containing 39.0% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17500, and the acid value was 54 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-9) containing 38.8% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17000, and the acid value was 53 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-10) containing 38.9% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17500, and the acid value was 54 mgKOH / g.
  • a separable flask equipped with a cooling tube was prepared as a reaction vessel.
  • a monomer composition in a monomer dropping tank 15 g of BzMI, 44.5 g of AA, 20.5 g of OPPE, 1 mol ethoxylated phenylphenol acrylate (trade name “A-LEN-10”, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter A-LEN 20 g) (also referred to as ⁇ 10), 2 g of PBO, 42 g of PGMEA, and 18 g of PGMEA were added and mixed with stirring.
  • nDM 2 g
  • 18 g of PGMEA 18 g
  • 8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
  • the monomer composition and the chain transfer agent solution were added dropwise.
  • the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C.
  • PBO 0.5g was added 30 minutes after the completion of the dropping.
  • the temperature of the reaction vessel was raised to 115 ° C.
  • 69 g of GMA, 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerization inhibitor, and 0.5 g of DMBA, 16 g of PGMEA, and 6 g of PGME are used as catalysts.
  • the reaction was performed at 110 ° C. for 1 hour and at 115 ° C.
  • copolymer solution (A-11) containing 39.1% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18100, and the acid value was 54 mgKOH / g.
  • nDM 2 g
  • 18 g of PGMEA 18 g
  • 8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
  • the monomer composition and the chain transfer agent solution were added dropwise.
  • the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C.
  • PBO 0.5g was added 30 minutes after the completion of the dropping.
  • the temperature of the reaction vessel was raised to 115 ° C.
  • 69 g of GMA, 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerization inhibitor, and 0.5 g of DMBA, 16 g of PGMEA, and 6 g of PGME are used as catalysts.
  • the reaction was performed at 110 ° C. for 1 hour and at 115 ° C.
  • nDM 2 g
  • 18 g of PGMEA 18 g
  • 8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
  • the monomer composition and the chain transfer agent solution were added dropwise.
  • the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C.
  • PBO 0.5g was added 30 minutes after the completion of the dropping.
  • the temperature of the reaction vessel was raised to 115 ° C.
  • 69 g of GMA, 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerization inhibitor, and 0.5 g of DMBA, 16 g of PGMEA, and 6 g of PGME are used as catalysts.
  • the reaction was performed at 110 ° C. for 1 hour and at 115 ° C.
  • copolymer solution (A-13) containing 39.0% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18000, and the acid value was 53 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-14) containing 38.8% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18100, and the acid value was 56 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-15) containing 39.5% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18200, and the acid value was 54 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-16) containing 39.1% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17800, and the acid value was 56 mgKOH / g.
  • nDM 2 g
  • 18 g of PGMEA 18 g
  • 8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
  • the monomer composition and the chain transfer agent solution were added dropwise.
  • the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C.
  • PBO 0.5g was added 30 minutes after the completion of the dropping.
  • the temperature of the reaction vessel was raised to 115 ° C.
  • 69 g of GMA, 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a polymerization inhibitor, and 0.5 g of DMBA, 16 g of PGMEA, and 6 g of PGME are used as catalysts.
  • the reaction was performed at 110 ° C. for 1 hour and at 115 ° C.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-18) containing 39.4% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 17400, and the acid value was 54 mgKOH / g.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • the reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C.
  • copolymer solution (A-20) containing 38.6% by weight of an acrylic resin.
  • the weight average molecular weight (Mw) of the acrylic resin was 18200, and the acid value was 56 mgKOH / g.
  • Example 1 89 g of the copolymer solution (A-1) (that is, 35 g of acrylic resin), 65 g of tripentaerythritol octaacrylate (trade name “Biscoat # 802”, manufactured by Osaka Organic Chemical Co., Ltd.) as a polyfunctional monomer, and photopolymerization start To a mixture of 1.75 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (trade name “IRGACURE® 907”, manufactured by BASF Japan Ltd.) as an agent, PGMEA was added so that the solid content concentration was 35% by weight, and the mixture was filtered through a filter having a pore size of 0.5 ⁇ m to prepare a photosensitive resin composition for a photospacer.
  • A-1 that is, 35 g of acrylic resin
  • 65 g of tripentaerythritol octaacrylate trade name “Biscoat # 802”, manufactured by Os
  • the photosensitive resin composition for photospacers was applied onto a 10 cm square glass substrate with a spin coater, and dried in an oven at 80 ° C. for 3 minutes. After drying, the strength (50 mJ / cm 2 ) by a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) with a photomask placed at a distance of 100 ⁇ m from the coating film and equipped with a 2.0 kW ultrahigh pressure mercury lamp. Ultraviolet rays were irradiated at 365 nm illuminance conversion).
  • Example 2 to 26 A photospacer was formed in the same manner as in Example 1 except that the composition of the photosensitive resin composition for photospacer was changed to the composition shown in Table 2, and subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • Table 2 dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) is represented as “DPHA”, and pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) is represented as “PETA”.
  • DPHA dipentaerythritol hexaacrylate
  • PETA pentaerythritol tetraacrylate
  • Examples 4 to 8 a UV absorber was further added.
  • Example 27 89 g of the copolymer solution (A-1) (that is, 35 g of acrylic resin), 65 g of tripentaerythritol octaacrylate (trade name “Biscoat # 802”, manufactured by Osaka Organic Chemical Co., Ltd.) as a polyfunctional monomer, and a wavelength of 290 nm to 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (trade name “IRGACURE”) is used as a photopolymerization initiator (first photopolymerization initiator) having a maximum absorption wavelength at 380 nm.
  • A-1 that is, 35 g of acrylic resin
  • 65 g of tripentaerythritol octaacrylate trade name “Biscoat # 802”, manufactured by Osaka Organic Chemical Co., Ltd.
  • IRGACURE 2-Methyl-1- [4- (methylthio) phenyl] -2
  • the photosensitive resin composition for a photospacer was applied onto a 10 cm square glass substrate with a spin coater and dried in an oven at 80 ° C. for 3 minutes. After drying, the strength (50 mJ / cm 2 ) by a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) with a photomask placed at a distance of 100 ⁇ m from the coating film and equipped with a 2.0 kW ultrahigh pressure mercury lamp. Ultraviolet rays were irradiated at 365 nm illuminance conversion).
  • Example 28 to 38 A photospacer was formed in the same manner as in Example 27 except that the composition of the photosensitive resin composition for photospacer was changed to the composition shown in Table 4, and subjected to the same evaluation as in Example 27.
  • the results are shown in Table 4.
  • Table 4 dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) is represented as “DPHA”, and pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) is represented as “PETA”.
  • a thinner photospacer can be formed by using a photosensitive resin composition for photospacer containing a UV absorber.
  • the photospacer formed by the photosensitive resin composition for a photospacer of the present invention is thin but has sufficient breaking strength.
  • the photosensitive resin composition for photospacers of the present invention can be suitably used for the production of spacers for liquid crystal cells.

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Abstract

L'invention concerne une composition de résine photosensible pour une entretoise photo qui présente d'excellentes propriétés d'adhésion à un substrat, laquelle est capable de former une entretoise photo présentant une reprise élastique et une résistance à la rupture excellentes et avec laquelle peu de résidu de développement est généré. Cette composition de résine photosensible pour une entretoise photo comprend une résine acrylique comme polymère liant, ladite résine acrylique ayant des groupes fonctionnels répétitifs ayant une structure cyclique dans leur chaîne principale, et des groupes fonctionnels répétitifs ayant au moins deux groupes oxyalkylènes dans une de leurs chaînes ramifiées. Dans un mode de réalisation de la présente invention, cette composition de résine photosensible pour une entretoise photo comprend : un monomère multifonctionnel ; un premier initiateur de photopolymérisation ayant une longueur d'onde d'absorption maximale comprise entre 290 nm et 380 nm ; et un second initiateur de photopolymérisation ayant une longueur d'onde d'absorption maximale comprise entre 230 nm et 290 nm.
PCT/JP2013/073765 2012-09-05 2013-09-04 Composition de résine photosensible pour entretoise photo et entretoise photo WO2014038576A1 (fr)

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CN104641295A (zh) 2015-05-20
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