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WO2019059169A1 - Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille - Google Patents

Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille Download PDF

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Publication number
WO2019059169A1
WO2019059169A1 PCT/JP2018/034421 JP2018034421W WO2019059169A1 WO 2019059169 A1 WO2019059169 A1 WO 2019059169A1 JP 2018034421 W JP2018034421 W JP 2018034421W WO 2019059169 A1 WO2019059169 A1 WO 2019059169A1
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Prior art keywords
resin composition
photosensitive resin
general formula
alkali
transparent photosensitive
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PCT/JP2018/034421
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English (en)
Japanese (ja)
Inventor
橋本昇太
國富瑠美子
西山雅仁
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東レ株式会社
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Priority to CN201880060412.0A priority Critical patent/CN111149058B/zh
Priority to JP2018550620A priority patent/JPWO2019059169A1/ja
Publication of WO2019059169A1 publication Critical patent/WO2019059169A1/fr

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    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a transparent photosensitive resin composition, a photospacer, a liquid crystal display, a method of manufacturing a photospacer, a method of manufacturing a liquid crystal display, and use of the transparent photosensitive resin composition for lens scan exposure.
  • Liquid crystal display devices are used in various applications such as laptop computers, personal digital assistants, smart phones, digital cameras and desktop monitors, taking advantage of characteristics such as light weight, thinness and low power consumption.
  • the liquid crystal display device includes a liquid crystal layer capable of displaying an image according to a predetermined orientation between a color filter substrate and a TFT (Thin Film Transistor) substrate, and the distance (cell gap) between these substrates is made uniform. Maintaining is one of the important factors affecting image quality.
  • spacer particles such as glass or alumina having a predetermined particle diameter have been used. Since these spacer particles are randomly scattered on the substrate, there is a problem such as display unevenness due to film thickness variation.
  • Patent Document 1 a photosensitive film for resin spacer formation, which is used to form a resin spacer for liquid crystal display comprising a support film and a photosensitive resin layer having a thickness of 1 to 10 ⁇ m, has been proposed (for example, , Patent Document 1).
  • Patent Document 1 a photosensitive film for resin spacer formation, which is used to form a resin spacer for liquid crystal display comprising a support film and a photosensitive resin layer having a thickness of 1 to 10 ⁇ m.
  • a photosensitive resin composition for a spacer comprising, as a main component, a liquid crystal panel substrate (see, for example, Patent Document 2), an alkali-soluble resin, a photopolymerization initiator, and a polymerizable monomer, which is 60% or more.
  • a photosensitive resin composition for spacers see, for example, Patent Document 3) or the like, which is characterized in that the acrylic equivalent of the whole of these photosensitive resin compositions is 200 or less has been proposed.
  • the mother glass substrate is increasing in size, and a constant speed is provided by the substrate transfer means as a technique for exposing a substrate having a wide exposure area using a small mask.
  • the exposure light from the continuous light source is irradiated through the opening of the mask provided on the light path of the exposure optical system in the exposure unit to the substrate being transported in a predetermined direction.
  • a scan exposure method for transferring an image has been proposed (see, for example, Patent Document 4).
  • Methods of increasing the elastic deformation rate of the columnar spacers described in Patent Documents 2 and 3 include a method in which a large amount of a monomer having a large number of functional groups is contained in the photosensitive resin composition.
  • the coating film of the base resin composition has high fluidity even after drying, and unevenness in film thickness easily occurs in the production process, so that the height of the photospacer tends to vary.
  • proximity type exposure which is a conventional exposure type
  • the photo spacers tend to be connected due to the influence of diffracted light.
  • multipatterning in which one plate is shifted to perform multiple exposure has been proposed.
  • the film thickness of the next exposed portion becomes thinner due to the flow of the pre-baking film after the first exposure, and there is a problem that the dispersion of the height of the photo spacer becomes large.
  • the present invention is directed to a transparent photosensitive resin composition which can suppress the variation of the height of the photospacer and can form a photospacer which is resistant to plastic deformation, that is, having a high elastic recovery ratio. It is an object of the present invention to provide a photo spacer, a liquid crystal display device, a method of manufacturing the photo spacer, a method of manufacturing the liquid crystal display device, and use of the transparent photosensitive resin composition for lens scan exposure.
  • the present invention mainly has the following composition.
  • a transparent photosensitive resin composition comprising at least an alkali soluble resin, a photopolymerization initiator and a polymerizable monomer, wherein the alkali soluble resin is A) a structural unit represented by the following general formula (1): B) Structural units represented by the following general formula (2): C) having a structural unit represented by the following general formula (3),
  • the transparent photosensitive resin composition whose ethylenically unsaturated group equivalent of the said alkali-soluble resin is 400 g / mol or less.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group.
  • m and n each independently represent an integer of 1 to 4.
  • Y has an aryl group having 6 to 11 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, or a substituent. And an optionally substituted C 3-10 cycloalkyl group.
  • the transparent photosensitive resin composition of the present invention even when exposure is performed by a lens scan method or a proximity method in which the variation in height of the photo spacer tends to be large, the high elastic recovery rate suppressed the variation in height. Can be formed.
  • the transparent photosensitive resin composition of the present invention contains at least an alkali-soluble resin, a photopolymerization initiator and a polymerizable monomer.
  • photosensitive resin composition contains at least an alkali-soluble resin, a photopolymerization initiator and a polymerizable monomer.
  • the exposed portion can be photocured to be insolubilized in an alkali developer, and by containing an alkali-soluble resin, it is not exposed using an alkali developer. Since the part can be removed, the desired pattern can be formed by exposure and development.
  • the "transparent" in the present invention means that the light transmittance at a wavelength of 400 to 700 nm is 80% or more when the photosensitive resin composition is photocured to form a cured film having a thickness of 3 ⁇ m.
  • the photosensitive resin composition of the present invention is preferably substantially free of a colorant such as a pigment or a dye in order to increase the light transmittance at a wavelength of 400 to 700 nm.
  • the alkali-soluble resin in the present invention means a resin having a structural unit represented by the general formula (1) described later. By having a carboxyl group, the solubility in an alkali developer can be enhanced.
  • the alkali-soluble resin in the present invention is represented by A) a structural unit represented by the following general formula (1), B) a structural unit represented by the following general formula (2), and C) the following general formula (3)
  • A) a structural unit represented by the following general formula (1) the solubility of the resin in an alkali developer can be improved.
  • B) a structural unit represented by the following general formula (2) By introducing an ethylenically unsaturated group into the side chain of the alkali-soluble resin by having a structural unit represented by the following general formula (2), the sensitivity in exposure and development and the elastic recovery of the photospacer are improved.
  • Can. By having a structural unit represented by the following general formula (3), variation in height of the photo spacer can be suppressed.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 1 is preferably a methyl group, which can increase the viscosity of the pre-baked film and can further suppress variations in height.
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group.
  • m and n each independently represent an integer of 1 to 4.
  • Y has an aryl group having 6 to 11 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, or a substituent. And an optionally substituted C 3-10 cycloalkyl group.
  • Y is preferably a cycloalkyl group having a carbon number of 3 to 10 which may have a substituent, more preferably a cyclohexyl group, which can further increase the viscosity of the pre-baked film and can further suppress the variation in height.
  • the alkali-soluble resin in the present invention is, for example, a copolymer component constituting the structural unit represented by the general formula (1), a copolymer component constituting the structural unit represented by the general formula (2), and the general It can obtain by copolymerizing the copolymerization component which comprises the structural unit represented by Formula (3). Furthermore, other copolymerizable components may be copolymerized.
  • An ethylenically unsaturated compound having a glycidyl group is subjected to an addition reaction with the carboxyl group of the acrylic polymer having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3)
  • the structural unit represented by the general formula (2) can be introduced.
  • the structural unit represented by the general formula (2) can be introduced also by the addition reaction of an ethylenically unsaturated compound, an ethylenically unsaturated compound having an isocyanate group, and an ethylenically unsaturated compound having a hydroxyl group. it can.
  • (meth) acrylic acid etc. are mentioned, for example. Two or more of these may be used. Among these, methacrylic acid is preferable, and the viscosity of the pre-baked film can be further increased, and the variation in height can be further suppressed.
  • (meth) acrylic acid As a copolymerization component which comprises the structural unit represented by said General formula (2), (meth) acrylic acid; glycidyl (meth) acrylate, 2-isocyanatoethyl methacrylate, 2-hydroxyethyl (meth) acrylate, for example Etc. Two or more of these may be used. Among these, it is preferable to add glycidyl (meth) acrylate to (meth) acrylic acid.
  • N-benzyl maleimide N- phenyl maleimide, N- cyclohexyl maleimide etc. are mentioned, for example. Two or more of these may be used. Among these, N-cyclohexyl maleimide is preferable, and the viscosity of the pre-baked film can be further increased, and the variation in height can be further suppressed.
  • copolymerization components include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate ( (Meth) acrylic acid sec-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid n-pentyl, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, benzyl ( Unsaturated carboxylic acid alkyl ester such as meta) acrylate and isobornyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester such as aminoethyl acrylate, Polyvalent carboxylic acid such as mono (2- (meth) acryloyloxyethyl) phthalate Acid monoester; st
  • the amount of the structural unit represented by the general formula (3) is preferably 10 to 23 mol%.
  • the dry viscosity can be further increased when the amount of the structural unit represented by the general formula (3) is 10 mol% or more, and the viscosity of the pre-baked film can be further increased when the amount is 15 mol% or more.
  • the ethylenic unsaturated bond equivalent and an acid value can be easily adjusted to the preferable range mentioned later as the structural unit quantity represented by the said General formula (3) is 23 mol% or less.
  • the ethylenically unsaturated group equivalent of the alkali-soluble resin in the present invention is 400 g / mol or less.
  • the ethylenically unsaturated group equivalent exceeds 400 g / mol, the crosslink density of the photo spacer decreases and the elastic recovery rate decreases.
  • 360 g / mol or less is preferable and 300 g / mol or less of the ethylenically unsaturated group equivalent of alkali-soluble resin is more preferable.
  • the ethylenically unsaturated group equivalent refers to the number of grams per mole of the ethylenically unsaturated group, and the smaller the value, the larger the amount of the ethylenically unsaturated group contained.
  • the higher the content ratio of the structural unit represented by the general formula (2) B having an ethylenically unsaturated group the smaller the equivalent amount of the ethylenically unsaturated group.
  • the ethylenically unsaturated group equivalent of the alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound having the ethylenically unsaturated group.
  • the ethylenically unsaturated group equivalent can be calculated by measuring the iodine value by the method described in paragraph 6.0 of the test method of JIS K 0070: 1992.
  • the weight average molecular weight ("Mw") of the alkali-soluble resin in the present invention is preferably 10,000 to 100,000. By setting Mw to 10,000 or more, the viscosity of the pre-baked film can be increased, and the variation in height can be further suppressed. Mw is more preferably 20,000 or more. On the other hand, by setting Mw to 100,000 or less, unevenness of the pattern surface can be suppressed, and the surface shape of the pattern can be improved. Mw is more preferably 80,000 or less.
  • Mw of the alkali-soluble resin in the present invention is a value converted by standard polystyrene, and can be measured using gel permeation chromatography.
  • the acid value of the alkali-soluble resin in the present invention is preferably 60 to 100 mg KOH / g. By setting the acid value to 60 mg KOH / g or more, the height variation can be further reduced.
  • the acid value is more preferably 65 mg KOH / g or more.
  • the acid value is more preferably 95 mg KOH / g or less.
  • the acid value of the alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound having a carboxyl group.
  • the acid value of the alkali-soluble resin in the present invention can be determined by the neutralization titration method of test method section 3.1 of JIS K 0070: 1992.
  • an alkali-soluble resin solution with a solid content concentration of about 30% by mass 5 g of the alkali-soluble resin solution is put in an aluminum cup ( ⁇ 45 mm) and heated at 130 ° C. for 1 hour to remove the solvent.
  • an alkali-soluble resin solid content in an amount necessary for measuring the acid value.
  • the alkali-soluble resin When the alkali-soluble resin is obtained by adding glycidyl (meth) acrylate to (meth) acrylic acid, unreacted glycidyl (meth) acrylate may remain together with the alkali-soluble resin.
  • the residual amount of glycidyl (meth) acrylate is preferably 0.001 to 0.500% by mass per solid content in the method determined above. By setting the residual amount of glycidyl (meth) acrylate to 0.001% by mass or more, the heating time for removing glycidyl (meth) acrylate does not need to be long, and the gelation of the alkali-soluble resin due to heating is suppressed be able to.
  • the remaining amount of glycidyl (meth) acrylate of the alkali-soluble resin can be determined from the amount of glycidyl (meth) acrylate measured from the alkali-soluble resin solution using gas chromatography and the solid content concentration of the alkali resin solution .
  • the content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 25 to 82 parts by mass with respect to 100 parts by mass of a polymerizable monomer described later.
  • the content of the alkali-soluble resin is more preferably 34 parts by mass or more.
  • the elastic recovery rate can be further improved. 66 mass parts or less are more preferable, 62 mass parts or less are more preferable, 55 mass parts or less are more preferable, and 40 mass parts or less are more preferable as content of alkali-soluble resin.
  • the photopolymerization initiator in the present invention refers to a compound which is decomposed and / or reacted by light (including ultraviolet light or electron beam) to generate a radical.
  • the photosensitive resin composition of the present invention can improve sensitivity by containing a photopolymerization initiator.
  • the photopolymerization initiator include oxime ester compounds, alkylphenone compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, acylphosphine oxide compounds, and titanocene compounds.
  • a compound etc. are mentioned. Two or more of these may be contained.
  • oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-) Methyl benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- ⁇ 2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl ⁇ -9H-Carbazol-3-yl]-, 1- (O-acetyloxime), “Optomer” (registered trademark) N-1919, NCI-831, NCI-930 (
  • alkylphenone compounds examples include 2,2-diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (dimethylamino) -2-[(4) -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, ⁇ -hydroxyisobutylphenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Examples thereof include phenyl-propan-1-one, “IRGACURE” (registered trademark) 907 (manufactured by BASF Japan Ltd.), and the like.
  • benzophenone compounds include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso.
  • Pirthioxanthone, 1-chloro-4-propylthioxanthone, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
  • imidazole compounds examples include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like.
  • benzothiazole compound examples include 2-mercaptobenzothiazole and the like.
  • benzoxazole compounds examples include 2-mercaptobenzoxazole and the like.
  • acyl phosphine oxide compound examples include 2,4,6-trimethyl benzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide and the like.
  • titanocene compounds examples include bis ( ⁇ 5-2, 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like.
  • oxime ester compounds and alkylphenone compounds are preferable.
  • oxime ester compounds “Adekaqules” (registered trademark) N-1919 is more preferable, and among the alkylphenone compounds, “IRGACURE” (registered trademark) 907 is more preferable.
  • the content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably 2 to 30 parts by mass, more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the total content of the alkali-soluble resin and the polymerizable monomer. preferable.
  • the polymerizable monomer in the present invention refers to a monomer having at least one ethylenically unsaturated bond.
  • examples of the polymerizable monomer include monofunctional or polyfunctional monomers and oligomers. Two or more of these may be contained.
  • polyfunctional monomers are preferable.
  • polyfunctional polymerizable monomer for example, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis 3-Methyl-4- (3-acryl
  • the photosensitive resin composition of the present invention comprises a filler, a sensitizer, a UV absorber, an adhesion improver, a surfactant, a polymerization inhibitor, a polymer compound other than the above-mentioned alkali-soluble compound, an organic acid, an organic amino compound, You may contain additives and solvents, such as a hardening agent.
  • the photosensitive resin composition of the present invention can further increase the viscosity after drying of the pre-baked film, and can further suppress the height variation.
  • the filler include inorganic oxide particles such as silica, alumina, titania and barium sulfate; metal particles; and resin particles such as acrylic, styrene, silicone and fluorine-containing polymer. Two or more of these may be contained. Among these, silica particles are preferable from the viewpoint of particle diameter and dispersibility.
  • the average particle diameter in terms of specific surface area of the filler is preferably 4 to 120 nm. When the average particle diameter of the filler is 4 nm or more, the height variation can be further suppressed. On the other hand, when the particle diameter is 120 nm or less, unevenness of the pattern surface can be suppressed, and the surface shape of the pattern can be improved.
  • the photosensitive resin composition of the present invention can improve sensitivity by containing a sensitization auxiliary.
  • the sensitization assistant include aromatic or aliphatic tertiary amines and the like.
  • the photosensitive resin composition of the present invention can easily form a fine, short, tapered photospacer by containing an ultraviolet light absorber.
  • an ultraviolet light absorber organic compound UV absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds are preferable from the viewpoint of transparency and non-coloring property. Two or more of these may be contained. Among these, benzotriazole compounds are preferable.
  • benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol and 2- (2H-benzotriazol-2-yl) -4--6-bis (1-methyl-1). -Phenylethyl) phenol, 2- [5 chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butylphenol), 2,4-di-tert-butyl-6- (5-chloro) Benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H- Benzotriazol-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) ) -6-dodecyl-4-methylphenol, 2 [2-hydroxy-3- (3,4,5,
  • benzophenone compounds include octabenzone, 2-hydroxy-4-n-octoxybenzophenone and the like.
  • triazine compounds examples include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.
  • the content of the ultraviolet light absorber in the photosensitive resin composition of the present invention is preferably 0.3 to 10% by mass in the solid content.
  • the tapered portion can be further shortened.
  • content of a ultraviolet absorber 2 mass% or more is more preferable.
  • the sensitivity can be maintained high by setting the content of the ultraviolet absorber to 10% by mass or less.
  • content of a ultraviolet absorber 8 mass% or less is more preferable.
  • solid content means the component except the solvent contained in the photosensitive resin composition.
  • adhesion improver for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino) Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,
  • the content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass in the solid content.
  • the content of the adhesion improver is more preferably 0.5% by mass or more.
  • aggregation of the alkali-soluble resin and the polymerizable monomer can be suppressed by setting the content of the adhesion improver to 20% by mass or less.
  • the content of the adhesion improver is more preferably 10% by mass or less.
  • anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine and the like; cationic surfactants such as stearyl amine acetate, lauryl trimethyl ammonium chloride and the like; lauryl dimethyl amine oxide, lauryl Amphoteric surfactants such as carboxymethyl hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate; perfluorobutyl sulfonate, perfluoroalkyl group-containing Carboxylic acid salt, perfluoroalkyl group-containing trimethyl ammonium salt, perfluoroalkyl group-containing phosphoric acid ester, or perfluoroalkyl ether Fluorine-based surfactants such as lenoxide adducts; polyether-modified polymethylalkyls
  • the content of the surfactant in the photosensitive resin composition of the present invention is preferably 0.001 to 10% by mass in the solid content.
  • the coatability of the photosensitive resin composition can be improved by setting the content of the surfactant to 0.001% by mass or more.
  • the content of the surfactant is more preferably 0.01% by mass or more.
  • by setting the content of the surfactant to 10% by mass or less unevenness of the pattern surface can be suppressed, and the surface shape of the pattern can be improved.
  • content of surfactant 1 mass% or less is more preferable.
  • polymerization inhibitor examples include hydroquinone, tert-butyl hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl) and the like.
  • the content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.01 to 0.5% by mass in the solid content.
  • the content of the polymerization inhibitor is preferably 0.01 to 0.5% by mass in the solid content.
  • polymer compound other than the alkali-soluble resin examples include acrylic resins having no structural unit represented by the general formulas (1) to (3), alkyd resin, melamine resin, polyvinyl alcohol, polyester, polyether, polyamide , Polyamide imide, polyimide, polyimide precursor and the like. Two or more of these may be contained.
  • solvent examples include ether solvents, ester solvents, alcohol solvents, ketone solvents, xylene, ethylbenzene, solvent naphtha and the like. Two or more of these may be contained.
  • ether solvents examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether and the like.
  • propylene glycol monomethyl ether, propylene glycol monoethyl ether, and diethylene glycol methyl ethyl ether are preferable.
  • ester solvent for example, benzyl acetate, ethyl benzoate, ⁇ -butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-butyl acetate, 3-methoxy-3-methyl ester -Butyl acetate, diethyl oxalate, ethyl acetoacetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl 3-ethoxy propionate, 2-ethyl butyl acetate, isopentyl propionate, propylene glycol monomethyl ether propio Nitrate, propylene glycol monoethyl ether acetate, pentyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol Coulter tert
  • alcohol solvents examples include butanol, 3-methyl-2-butanol and 3-methyl-3-methoxybutanol.
  • ketone solvents examples include cyclopentanone and cyclohexanone.
  • the photosensitive resin composition of the present invention is coated to a film thickness of 3 ⁇ m after curing, dried under reduced pressure for 200 seconds under conditions of 25 ° C. and 45 Pa, and then heat dried in an oven at 105 ° C. for 10 minutes at 23 ° C. It is preferable that the viscosity in the above becomes 1 ⁇ 10 3 to 1 ⁇ 10 8 Pa ⁇ s. By having such viscosity, it can be used suitably for the manufacturing method of the photo spacer mentioned later. Here, with the viscosity at 23 ° C.
  • the photosensitive resin composition of the present invention forms a truncated cone-shaped photospacer having a diameter of 6 ⁇ m at the top and a diameter of 9 ⁇ m at the bottom, and a height of 3 ⁇ m at the bottom, and the elastic recovery rate when a load of 50 mN is applied. It is preferably 70% or more.
  • variation in the height of the spacer at the time of cell pressure bonding is more suppressed as an elastic restoration rate is 70% or more, and the display nonuniformity by the plastic deformation of a photo spacer can be reduced more.
  • the elastic recovery rate is more preferably 73% or more.
  • the above shape is a typical shape of the photo spacer, and the above load is an example of the load that the photo spacer receives during manufacture or use. According to this method, the degree of plastic deformation of the photosensitive resin composition used to form the photospacer can be relatively evaluated.
  • FIG. 1 shows a schematic view of an example of a hysteresis curve that represents the elastic properties of the photo spacer.
  • a hysteresis curve of the load applied to the photo spacer and the deformation amount D of the photo spacer as shown in FIG. 1 is obtained.
  • the elastic recovery rate of the photospacer (((Ha-Hb) / Ha) ⁇ 100) is obtained. It can be calculated.
  • photosensitive resin composition of the present invention it is preferable to use the photosensitive resin composition of the present invention described above in order to make the elastic recovery rate when forming a photo spacer into the above range, and in particular, the ethylenically unsaturated group equivalent is in the above-mentioned preferred range Photosensitive resin compositions are more preferred.
  • the photosensitive resin composition of the present invention comprises an alkali-soluble resin, a photopolymerization initiator and a polymerizable monomer, and, if necessary, other additives such as a surfactant, a polymerization inhibitor, a solvent, a UV absorber and the like, as desired. It can be obtained by mixing in
  • the photosensitive resin composition of the present invention can be preferably used for exposure of a lens scan method because height variations can be suppressed, and can be more preferably used for formation of a photo spacer by lens scan exposure.
  • the shape of the photo spacer is preferably a frusto-conical shape for high definition of the color filter, and the diameter of the upper base is preferably 15 ⁇ m or less.
  • the ratio of the diameter of the upper base to the diameter of the lower (upper base / lower lower) is preferably 0.3 to 2.0.
  • the photosensitive resin composition of the present invention described above is preferably coated on a substrate and dried to obtain a pre-baked film, and the pre-baked film is preferably subjected to lens scan exposure and development to form a photospacer. Furthermore, it is preferable to heat-process and harden the coating film pattern after image development.
  • the substrate examples include transparent substrates such as glass and polymer films.
  • Examples of the method for applying the photosensitive resin composition include a dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, and the like.
  • drying under reduced pressure heating drying using an oven or a hot plate (pre-baking), etc.
  • the heating temperature is preferably 100 ° C. or less from the viewpoint of suppressing re-condensation of the drying solvent on the inner wall of the reduced pressure chamber.
  • the reduced pressure drying pressure is preferably equal to or less than the vapor pressure of the solvent contained in the photosensitive resin composition, and is preferably 1 to 1000 Pa.
  • the reduced pressure drying time is preferably 10 to 600 seconds.
  • pre-baking the heating temperature is generally 60 to 200 ° C., and the heating time is generally 1 to 60 minutes.
  • the viscosity at 23 ° C. of the pre-baked film is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 Pa ⁇ s.
  • the flowability of the pre-baked film is appropriately suppressed, and the process of transporting the pre-baked film, the exposure process, and the heating and drying (post-baking) process is performed.
  • the occurrence of unevenness can be further suppressed.
  • the viscosity at 23 ° C. is more preferably 1 ⁇ 10 5 Pa ⁇ s or more.
  • the developability can be improved by exposing the pre-baked film having a viscosity of 1 ⁇ 10 8 Pa ⁇ s or less at 23 ° C.
  • the viscosity at 23 ° C. of the pre-baked film is determined by collecting 90 mm 3 or more of the pre-baked film and using a rheometer (MCR-302; Anton Paar Co., Ltd.) and a plate with a diameter of 15 mm.
  • the viscosity at 23 ° C when measured while raising the temperature from 20 ° C to 110 ° C at a temperature rising rate of 0.083 ° C / sec under the condition of frequency: 1 Hz, strain: 0.5%.
  • the temperature of the pre-baked film is heated to about 100 ° C. in the drying step in the process of producing the photospacer on the color filter substrate, it is general that it becomes about room temperature (about 23 ° C.) by cooling before exposure. It is. Therefore, in the present invention, attention was paid to the viscosity at 23 ° C. as the pre-baked film temperature during general exposure.
  • the obtained pre-baked film is preferably exposed to light through a mask to cure the exposed portion, and developed with an alkaline developer to remove the unexposed portion and to form a pattern.
  • Examples of the exposure method include proximity exposure, lens scan exposure, mirror projection exposure, stepper exposure and the like.
  • lens scan exposure excellent in high definition pattern processing on a large substrate is preferably used. Since the photosensitive resin composition of the present invention can suppress height variations, it can be suitably used for lens scan exposure in which height variations are likely to occur.
  • Examples of the lens scan exposure apparatus include FX-65S (manufactured by Nikon Corporation).
  • development with an alkaline developer is preferred.
  • an alkali developing solution an organic alkali developing solution, an inorganic alkali developing solution, etc. are mentioned.
  • an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide and the like is preferable.
  • an aqueous tetramethyl ammonium hydroxide aqueous solution and an aqueous amine solution such as methanolamine are preferable.
  • the content of the alkaline substance in the alkaline developer is preferably 0.02% by mass or more from the viewpoint of the development solubility of the unexposed area.
  • the developer preferably contains a surfactant to enhance the uniformity of development.
  • the developing solution temperature is preferably selected in the range of 18 to 40 ° C. because the developing speed changes depending on the temperature of the developing solution.
  • Examples of the development method include dip development, shower development, and paddle development. It is preferable to appropriately select the temperature and flow rate of the developer and the shower injection pressure, the water washing temperature after development, the flow rate and the shower injection pressure conditions. In order to remove the residue on the substrate, it is preferable to jet the developer or the washing water under high pressure, and the jetting pressure is preferably 0.01 MPa to 20 MPa.
  • Examples of the heat treatment apparatus for the coating film pattern after development include a hot air oven, a hot plate and the like.
  • the heating temperature is preferably 180 to 300 ° C., and the heating time is preferably 5 to 90 minutes.
  • the color filter substrate has the above-mentioned photo spacer and pixel of the present invention on the substrate. If necessary, it may have a black matrix, a planarizing film, a transparent electrode, an alignment film, and the like.
  • color filter substrate examples include those exemplified as a substrate for forming a photo spacer.
  • the pixel may contain a colorant, a resin, a polymerizable monomer, a photopolymerization initiator, other additives, and the like, and may be formed of a cured product of a composition including one or more of them.
  • the colorant include organic pigments, inorganic pigments, and dyes.
  • a resin, a polymerizable monomer, a photoinitiator, and other additives what was illustrated as a component of the transparent photosensitive resin composition of this invention is mentioned, for example.
  • Examples of the shape of the pixel include a rectangle, a stripe, a square, a polygon, and a wave.
  • the pixel width is preferably 1 ⁇ m or more from the viewpoint of increasing the area of the opening and improving the transmittance. On the other hand, from the viewpoint of displaying a more precise image, the pixel width is preferably 100 ⁇ m or less.
  • the film thickness of the pixel is preferably about 1 to 5 ⁇ m.
  • the BM has an effect of improving the contrast of a display image by blocking light between pixels.
  • the BM may be a color overlap BM formed by overlapping a part of pixels adjacent to each other, but in order to improve the display image by suppressing the level difference of the pixels and obtain high light shielding property, the resin and It is preferable to contain a light shielding material.
  • a resin a polyimide resin or an acrylic resin is preferable.
  • a light shielding agent titanium black, titanium nitride, titanium carbide, carbon black etc. are mentioned, for example. Further, it may contain an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant and the like.
  • the film thickness of the BM is preferably 0.5 ⁇ m or more, and more preferably 0.8 ⁇ m or more, from the viewpoint of improving the light shielding property and the resistance value.
  • the thickness of the BM is preferably 2.5 ⁇ m or less, and more preferably 2.0 ⁇ m or less, from the viewpoint of improving the flatness.
  • the planarizing film may be formed on the entire surface of the pixel or the BM, or may be selectively formed on a portion to be planarized.
  • the planarizing film is preferably made of a cured product of a thermosetting resin composition, and when the planarizing film is selectively formed, the planarizing film Is preferably made of a cured product of the photosensitive resin composition.
  • the planarizing film preferably contains a resin, and may further contain an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant, and the like.
  • the thickness of the planarizing film is preferably 0.5 ⁇ m or more, and more preferably 1.0 ⁇ m or more from the viewpoint of flatness and suppression of the elution of impurities from the pixels.
  • the thickness of the planarizing film is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, from the viewpoint of improving the transparency.
  • the color filter substrate of the present invention can be obtained by forming the photo spacer and the pixel of the present invention, as necessary, a black matrix, a planarizing film, etc. on the substrate.
  • Examples of the method of forming the pixel, the black matrix, and the planarizing film include a photolithography method, a printing method, and an electrodeposition method.
  • the liquid crystal display device of the present invention comprises the color filter substrate described above, a drive element side substrate disposed opposite to the color filter, a color filter substrate, and a liquid crystal alignment film provided on the drive element side substrate, respectively. It is preferable to have the photo spacer which keeps the cell gap between these liquid crystal aligning films uniform, and the liquid crystal with which it was filled in space. For example, when using a color filter substrate having a black matrix, it is preferable to have a photo spacer above the non-display area, ie, the black matrix.
  • the driving element side substrate may have a photo spacer, and in this case as well, it is preferable to have the photo spacer above the non-display area on the driving element side substrate.
  • resin films such as a polyimide, are preferable.
  • a method of manufacturing a liquid crystal display device using the color filter substrate described above It is preferable to have a step of manufacturing a photo spacer on the color filter substrate and / or the driving element side substrate by the above-mentioned manufacturing method. Specifically, the above-mentioned color filter substrate and the drive element side substrate are made to face each other, they are pasted together via a photo spacer, liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed. Finally, it is preferable to mount an IC driver or the like.
  • the liquid crystal display device has a liquid crystal alignment film, it is preferable to apply a polyimide liquid and heat-treat it, and then to carry out surface treatment by rubbing treatment or ultraviolet light treatment. From the viewpoint of suppressing the generation of fine dust and static electricity and orienting liquid crystal molecules uniformly in high definition, it is preferable to perform surface treatment by ultraviolet treatment.
  • the properties of the alkali-soluble resin were evaluated by the following method.
  • the solutions of alkali-soluble resins 1 to 13 obtained in Production Examples 1 to 13 are heated at 130 ° C. for 1 hour, the solid content concentration is calculated from the mass before and after heating, and the glycidyl (meth) acrylate amount and alkali soluble resin are obtained.
  • the amount of residual glycidyl (meth) acrylate was calculated from the solid content concentration of the solution.
  • Alkali-soluble Resin 1 72 g of methacrylic acid (MA), 40 g of N-cyclohexylmaleimide (CHMI), 30 g of methyl methacrylate (MMA), 3 g of 2,2'-azobis (2-methylbutyronitrile), 0.5 g of lauryl mercaptan And 220 g of propylene glycol monomethyl ether (PGME) were charged in a polymerization vessel and stirred at 90 ° C. for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100 ° C., and reaction was carried out by heating for 5 hours.
  • MA methacrylic acid
  • CHMI N-cyclohexylmaleimide
  • MMA methyl methacrylate
  • PGME propylene glycol monomethyl ether
  • the inside of the polymerization vessel is replaced with air, and 97 g of glycidyl methacrylate (GMA), 1.2 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol are added to the obtained reaction solution, and the reaction is carried out at 110 ° C.
  • PGME was added to obtain a solution of alkali-soluble resin 1 having a solid concentration of 29.5% by mass.
  • Mw of the obtained alkali-soluble resin 1 was 40,000, the ethylenically unsaturated group equivalent was 350 g / mol, the acid value was 85 mg KOH / g, and the amount of remaining GMA was 0.05% by mass.
  • MA constitutes the structural unit represented by the general formula (1)
  • GMA constitutes the structural unit represented by the general formula (2)
  • CHMI is represented by the general formula (3) Construct a structural unit to be represented.
  • Production Example 2 (Alkali-Soluble Resin 2) Solid content concentration 28.3 mass% in the same manner as in Production Example 1 except that the blending amount of MA is 69 g, the blending amount of CHMI is 25 g, the blending amount of MMA is 18 g, and the blending amount of GMA is 98 g.
  • a solution of alkali soluble resin 2 was obtained.
  • the Mw of the obtained alkali-soluble resin 2 was 43,000, the equivalent weight of the ethylenically unsaturated group was 300 g / mol, the acid value was 63 mg KOH / g, and the amount of residual GMA was 0.05 mass%.
  • Production Example 3 (Alkali Soluble Resin 3) A solution of alkali soluble resin 3 having a solid content concentration of 28.5% by mass was obtained in the same manner as in Production Example 1 except that the blending amount of MA was changed to 32 g and the blending amount of GMA to 31 g.
  • the Mw of the obtained alkali-soluble resin 3 was 39,000, the equivalent weight of the ethylenically unsaturated group was 600 g / mol, the acid value was 85 mg KOH / g, and the amount of residual GMA was 0.05% by mass.
  • Alkali Soluble Resin 4 A solution of alkali soluble resin 4 having a solid concentration of 31.8% by mass was obtained in the same manner as in Production Example 1 except that the blending amount of lauryl mercaptan was changed to 2.2 g.
  • the Mw of the obtained alkali-soluble resin 4 was 9,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 85 mg KOH / g, and the residual GMA ratio was 0.05% by mass.
  • Production Example 5 (Alkali Soluble Resin 5) A solution of alkali-soluble resin 5 having a solid content concentration of 31.0 mass% in the same manner as in Production Example 1 except that the blending amount of MA is 66 g, the blending amount of CHMI is 50 g, and the blending amount of GMA is 96 g. I got The Mw of the obtained alkali-soluble resin 5 was 38,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 50 mg KOH / g, and the amount of residual GMA was 0.05% by mass.
  • Production Example 6 (Alkali-soluble Resin 6) The solid content concentration is 30.4 mass% in the same manner as in Production Example 1 except that the blending amount of MA is 59 g, the blending amount of CHMI is 28 g, the blending amount of MMA is 19 g, and the blending amount of GMA is 70 g.
  • a solution of alkali soluble resin 6 was obtained.
  • the Mw of the obtained alkali-soluble resin 6 was 35,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 110 mg KOH / g, and the amount of residual GMA was 0.05% by mass.
  • Production Example 7 (Alkali-soluble Resin 7) 13 g of methacrylic acid (MA), 15 g of N-cyclohexylmaleimide (CHMI), 72 g of methyl methacrylate (MMA), 3 g of 2,2'-azobis (2-methylbutyronitrile), 0.5 g of lauryl mercaptan And 220 g of propylene glycol monomethyl ether (PGME) were charged in a polymerization vessel and stirred at 90 ° C. for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100 ° C., and reaction was carried out by heating for 5 hours.
  • MA methacrylic acid
  • CHMI N-cyclohexylmaleimide
  • MMA methyl methacrylate
  • PGME propylene glycol monomethyl ether
  • alkali-soluble resin 7 After 0.2 g of p-methoxyphenol was added and cooled to room temperature, PGME was added to obtain a solution of alkali-soluble resin 7 having a solid concentration of 29.1% by mass. Mw of the obtained alkali-soluble resin 7 was 37,000, and the acid value was 85 mg KOH / g.
  • Production Example 8 (Production of Alkali-Soluble Resin 8) Solid content as in Production Example 1 except that 70 g of MA, 12 g of MMA and 98 g of GMA were changed to 15 g of styrene (St) instead of CHMI. A solution of alkali soluble resin 8 having a concentration of 29.2% by mass was obtained. The Mw of the obtained alkali-soluble resin 8 was 35,000, the equivalent weight of the ethylenically unsaturated group was 285 g / mol, the acid value was 67 mg KOH / g, and the amount of residual GMA was 0.05% by mass.
  • Alkali-soluble Resin 9 A solution of alkali-soluble resin 9 having a solid concentration of 29.5% by mass was obtained in the same manner as in Production Example 1 except that 40 g of N-benzylmaleimide (BzMI) was used instead of CHMI. Mw of the obtained alkali-soluble resin 9 was 40,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 64 mg KOH / g, and the amount of remaining GMA was 0.05% by mass.
  • BzMI N-benzylmaleimide
  • Production Example 10 (Production of Alkali-Soluble Resin 10) A solution of alkali-soluble resin 10 having a solid concentration of 29.5% by mass was obtained in the same manner as in Production Example 1 except that 60 g of acrylic acid (AA) was used instead of MA.
  • the Mw of the obtained alkali-soluble resin 10 was 40,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 62 mg KOH / g, and the amount of remaining GMA was 0.05% by mass.
  • Alkali-soluble Resin 11 A solution of alkali soluble resin 11 having a solid concentration of 29.5% by mass was obtained in the same manner as in Production Example 1 except that the stirring time at 110 ° C. was changed to 8 hours. Mw of the obtained alkali-soluble resin 1 was 40,000, the equivalent weight of the ethylenically unsaturated group was 350 g / mol, the acid value was 64 mg KOH / g, and the residual GMA ratio was 0.02 mass%.
  • Production Example 12 (Alkali-soluble Resin 12) A solution of an alkali-soluble resin 12 was obtained in the same manner as in Production Example 1 except that the stirring time at 110 ° C. was changed to 5 hours. Mw of the obtained alkali-soluble resin 12 was 40,000, the ethylenically unsaturated group equivalent was 350 g / mol, the acid value was 64 mg KOH / g, and the residual GMA rate was 0.30 mass%.
  • Production Example 13 (Alkali-soluble Resin 13) The solid content concentration is 28.5 mass% in the same manner as in Production Example 1 except that the blending amount of MA is 50 g, the blending amount of CHMI is 30 g, the blending amount of MMA is 0 g, and the blending amount of GMA is 65 g.
  • the solution of alkali-soluble resin 13 was obtained. Mw of the obtained alkali-soluble resin 13 was 36,000, the equivalent weight of the ethylenically unsaturated group was 278 g / mol, the acid value was 93 mg KOH / g, and the amount of residual GMA was 0.05% by mass.
  • a 1.0 ⁇ m-thick black matrix consisting of a composition containing a polyimide resin and carbon black on the surface of an alkali-free glass substrate (OA-10; manufactured by Nippon Electric Glass Co., Ltd .; 50 mm ⁇ 70 mm, thickness 0.7 mm) To form a black matrix-attached substrate.
  • OA-10 alkali-free glass substrate
  • the black matrix-coated substrate produced by the above method is cleaned by exposure to light for 60 seconds using a UV / ozone apparatus (SSP 16-110; manufactured by Sen Special Light Source Co., Ltd.) and then planarized by spin coating.
  • a coating film material (NN 901; manufactured by JSR Corp.) was applied and dried to form a transparent flattening film having a thickness of 1.5 ⁇ m. This was dried by heating (prebaked) at 90 ° C. for 10 minutes, and irradiated with ultraviolet light until the saturated exposure amount was reached.
  • TMAH tetramethylammonium hydroxide
  • A-60 tetramethylammonium hydroxide
  • Kao aqueous solution
  • the substrate was heat-dried (post-baked) at 230 ° C. for 30 minutes to prepare a substrate with a planarized film.
  • a substrate with a flattened film on which a pre-baked film has been formed is cooled to room temperature, and an ultraviolet ray exposure machine (PEM-6M; made by Union Optical Co., Ltd.) equipped with a glass UV filter (UV-35; made by Asahi Techno Glass Co., Ltd.) , Collimation angle ⁇ : 2 °, i-line (365 nm) illuminance: 30 mW / cm 2 ), without using a negative photomask, each wavelength of i-line: 365 nm, h-line: 405 nm and g-line: 436 nm It exposed by the exposure amount (i-line conversion) of 24 mJ / cm ⁇ 2 > by using the ultraviolet-ray containing as an irradiation light.
  • PEM-6M made by Union Optical Co., Ltd.
  • an automatic developing apparatus (AD-2000; manufactured by Mikasa Co., Ltd.) is used. It was shower developed, further washed with water and air dried. Next, it was heat-dried (post-baked) in an oven at 230 ° C. for 30 minutes to prepare a substrate with a 3.00 ⁇ m thick photo-spacer film.
  • the light transmittance at a wavelength of 400 to 700 nm is measured with a C light source using a microspectrometer (LCF-100MA: manufactured by Otsuka Electronics Co., Ltd.) for the central portion of the substrate with a photospacer solid film, and the following criteria
  • the transparency of the photosensitive resin composition was evaluated by the following. I passed A.
  • B Light transmittance at wavelengths of 400 to 700 nm is less than 80%.
  • Viscosity of pre-baked film As a sample reproducing the viscosity characteristics of the pre-baked films obtained in Examples 1 to 13 and Comparative Examples 1 to 3, alkali-free glass substrates (OA-10; manufactured by Nippon Electric Glass Co., Ltd .; 50 mm ⁇ 70 mm, thickness 0) On the .7 mm), a pre-baked film was produced under the conditions of each example and comparative example.
  • the obtained pre-baked film is collected 90 mm 3 or more using a spatula, measured using a rheometer (MCR-302; Anton Paar Co., Ltd.
  • the total deformation amount Ha [ ⁇ m] and the plastic deformation amount Hb [ ⁇ m] were obtained from the obtained hysteresis curve, and the elastic recovery factor ((Ha ⁇ Hb / Ha) ⁇ 100) of the photo spacer was calculated.
  • the number average value measured about five places was computed, and the following standard evaluated. Passed AA, A and B C: elastic recovery rate less than 70%
  • B elastic recovery rate 70% or more and less than 72%
  • A elastic recovery rate 72% or more and less than 73%
  • AA elastic recovery rate 73% or more.
  • Example 1 (Preparation of Photosensitive Resin Composition 1) Solution of alkali-soluble resin 1 having a solid content concentration of 29.5% by mass obtained by Production Example 1: 21.13 parts by mass, dipentaerythritol pentaacrylate ("KAYARAD” (registered trademark) DPHA; Nippon Kayaku; below, “DPHA”) (ethylenically unsaturated group equivalent 100): 11.58 parts by mass, photopolymerization initiator “Adeka Acrulus” (trademark registered) N-1919; hereinafter, “N1919”: 0.36 parts by mass, “ IRGACURE “(registered trademark) 907 (manufactured by BASF Japan Ltd.); hereinafter," IC 907 “: 0.89 parts by mass, 2,4-diethylthioxanthone (" KAYACURE "(registered trademark) DETX-S; Nippon Kayaku ( Co., Ltd .; hereafter, "DETX”): 0.89 parts by mass, surfact
  • the substrate with a planarizing film obtained by the above-mentioned method is subjected to a cleaning treatment by exposure for 60 seconds using a UV / ozone apparatus (SSP 16-110; manufactured by Sen Special Light Source Co., Ltd.), and then a spin coater
  • SSP 16-110 manufactured by Sen Special Light Source Co., Ltd.
  • the photosensitive resin composition 1 was applied using (type 1HD2; manufactured by Mikasa Co., Ltd.). After drying under reduced pressure for 200 seconds under the conditions of temperature: 25 ° C., pressure: 45 Pa, heat drying (pre-baking) in an oven (PERFECTOVEN PV-210; Tabai Espec Corp.) for 10 minutes set at 105 ° C. It was cooled to form a pre-baked film.
  • the i-line 365 nm through a circular photomask with a diameter of 7 ⁇ m, using the planarizing film-attached substrate on which the pre-baked film has been formed. It exposed by the exposure amount (i-line conversion) of 30 mJ / cm ⁇ 2 > by making the ultraviolet-ray containing each wavelength of h line
  • an automatic developing apparatus (AD-2000; manufactured by Mikasa Co., Ltd.) is used. It was shower developed, further washed with water and air dried. Finally, it was heat-dried (post-baked) in an oven at 230 ° C. for 30 minutes to produce a photospacer with an upper bottom 6 ⁇ m, a lower bottom 9 ⁇ m, and a height 3 ⁇ m.
  • the ultraviolet exposure machine (PEM-6M; Union Optical Co., Ltd. product) which attached the glass-made UV filter (UV-35; Asahi Techno Glass Co., Ltd. product) to the substrate with a planarization film which formed the above-mentioned pre-baking film
  • the first exposure was performed using ultraviolet light including 405 nm and g-line: 436 nm wavelengths.
  • the negative photomask was shifted by a half pitch to perform subsequent exposure (proximity exposure multi-patterning).
  • an automatic developing apparatus (AD-2000; manufactured by Mikasa Co., Ltd.) is used. It was shower developed, further washed with water and air dried. Finally, it was heat-dried (post-baked) in an oven at 230 ° C. for 30 minutes to produce a photospacer with an upper bottom 6 ⁇ m, a lower bottom 9 ⁇ m, and a height 3 ⁇ m.
  • Examples 2 to 13, Comparative Examples 1 to 3 A photosensitive resin composition, a pre-baked film and a photo spacer were produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as shown in Table 2. The results evaluated in the same manner as in Example 1 are shown in Tables 3 to 5.
  • M520 in Tables 3 to 5 means the reaction product of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate with succinic anhydride (M520; manufactured by Toagosei Co., Ltd .; ethylenic unsaturated equivalent 104 g / Mol) is represented.
  • the transparent photosensitive resin composition of the present invention is suitably used as a material for forming a photo spacer of a liquid crystal display by lens scan exposure.

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  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Le but de la présente invention est de fournir : une composition de résine photosensible transparente qui permet la formation de photo-espaceurs dont la variation en hauteur est supprimée mais qui ne sont pas sensibles à une déformation plastique, autrement dit qui possèdent un haut taux de récupération élastique ; un photo-espaceur qui est obtenu à l'aide de cette composition de résine photosensible transparente ; un dispositif d'affichage à cristaux liquides ; un procédé de production d'un photo-espaceur ; un procédé de production d'un dispositif d'affichage à cristaux liquides ; et l'utilisation de cette composition de résine photosensible transparente pour une exposition par balayage de lentille. La présente invention concerne une composition de résine photosensible transparente qui contient au moins une résine soluble dans les alcalis, un amorceur de photopolymérisation et un monomère polymérisable, et dans laquelle : la résine soluble dans les alcalis a (A) un motif structural représenté par la formule générale (1), (B) un motif structural représenté par la formule générale (2), et (C) un motif structural représenté par la formule générale (3) ; et l'équivalent de groupe éthyléniquement insaturé de la résine soluble dans les alcalis est de 400 g/mol ou moins. (Dans la formule générale (1), R4 désigne un atome d'hydrogène ou un groupe méthyle.) (Dans la formule générale (2), R2 et R3 désignent chacun indépendamment un atome d'hydrogène ou un groupe méthyle ; et X désigne -CH2CH(OH)CH2O(C=O)-, -CH2CH2NH(C=O)O(CH2)mO(C=O)- ou -(CH2)nO(C=O)NHCH2CH2O(C=O)-, m et n désignant chacun indépendamment un nombre entier de 1 à 4.) (Dans la formule générale (3), Y désigne un groupe aryle éventuellement substitué comprenant de 6 à 11 atomes de carbone, un groupe aralkyle éventuellement substitué comprenant de 7 à 10 atomes de carbone ou un groupe cycloalkyle éventuellement substitué comprenant de 3 à 10 atomes de carbone.
PCT/JP2018/034421 2017-09-22 2018-09-18 Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille WO2019059169A1 (fr)

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CN201880060412.0A CN111149058B (zh) 2017-09-22 2018-09-18 透明感光性树脂组合物及其应用、光刻间隔物和液晶显示装置及其制造方法
JP2018550620A JPWO2019059169A1 (ja) 2017-09-22 2018-09-18 透明感光性樹脂組成物、フォトスペーサー、液晶表示装置、フォトスペーサーの製造方法、液晶表示装置の製造方法および透明感光性樹脂組成物のレンズスキャン露光への使用

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