[go: up one dir, main page]

WO2007013233A1 - Composition de résine photosensible pour élément d’affichage à cristaux liquides, filtre de couleur l’utilisant, procédé de fabrication du filtre de couleur, et élément d’affichage à cristaux liquides - Google Patents

Composition de résine photosensible pour élément d’affichage à cristaux liquides, filtre de couleur l’utilisant, procédé de fabrication du filtre de couleur, et élément d’affichage à cristaux liquides Download PDF

Info

Publication number
WO2007013233A1
WO2007013233A1 PCT/JP2006/312094 JP2006312094W WO2007013233A1 WO 2007013233 A1 WO2007013233 A1 WO 2007013233A1 JP 2006312094 W JP2006312094 W JP 2006312094W WO 2007013233 A1 WO2007013233 A1 WO 2007013233A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
liquid crystal
exposure
crystal display
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/312094
Other languages
English (en)
Japanese (ja)
Inventor
Daisuke Kashiwagi
Mitsutoshi Tanaka
Hirotaka Matsumoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2007528371A priority Critical patent/JPWO2007013233A1/ja
Publication of WO2007013233A1 publication Critical patent/WO2007013233A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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

Definitions

  • Photosensitive resin composition for liquid crystal display element for liquid crystal display element, color filter using the same, manufacturing method thereof, and liquid crystal display element
  • the present invention relates to a photosensitive resin composition for liquid crystal display elements, a method for producing a color filter using the resin composition, a color filter, and a liquid crystal display element comprising the color filter.
  • the present invention relates to a photosensitive resin composition for a liquid crystal display element useful for forming partition walls, spacers, pixels, a black matrix, etc. of a liquid crystal cell, a color filter produced using the resin composition,
  • the present invention relates to a method for producing a color filter using a resin composition, and a liquid crystal display device provided with the color filter produced thereby.
  • LCDs liquid crystal displays
  • a color image in a liquid crystal display is formed by the light passing through the color filter being colored in the hue of each pixel of the color filter, and the light of those colors is synthesized.
  • LCDs liquid crystal displays
  • Display characteristics are improved by increasing the pixel definition, improving the uniformity of display within the screen by correcting the mask error, increasing the contrast so that the difference between bright and dark images can be displayed more clearly, and increasing the speed. Response has been studied, especially reduction of ITO resistance.
  • a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and the distance between the substrates, that is, the thickness of the liquid crystal layer is maintained uniformly. Is one of the factors that determine image quality. To keep the thickness of the liquid crystal layer constant, a spacer with high positional accuracy has been formed by photolithography using a photosensitive resin composition. A spacer formed using such a photosensitive resin composition is called a photospacer.
  • the photosensitive resin composition used here is useful not only for spacers but also for the formation of partition walls, black matrixes, and further the pixels themselves of the liquid crystal cell pixels.
  • the production method is generally such that the photosensitive resin composition is exposed to cure the exposed area, and the unexposed part is exposed.
  • a photolithography method for forming a fine pattern by removing the film by development is known.
  • LDM laser direct imaging system
  • each of the light from the light irradiation means is controlled by a light modulation means having n picture elements for receiving and emitting light from the light irradiation means using laser light as a light source.
  • a spatial light modulation element that modulates in accordance with a signal, an enlargement imaging optical system for enlarging an image of light modulated by the spatial light modulation element, and a space disposed on an imaging surface of the enlargement imaging optical system;
  • a microlens array having a microlens array corresponding to each pixel portion of the light modulation element, and an imaging optical system that forms an image of the light that has passed through the microlens array on a pattern forming material or a screen.
  • An exposure apparatus provided is known (for example, see Non-Patent Document 1 and Patent Document 1).
  • LDI has the advantage that an expensive photomask is not required.
  • the above-mentioned LCDs are required to improve performance significantly, and at the same time, productivity (such as tact) is strictly required.
  • productivity such as tact
  • a VA mode with a wide viewing angle has recently been proposed (for example, see Non-Patent Document 2).
  • a low dielectric constant protrusion called a rib is formed on one or both of a pair of upper and lower transparent electrodes, or both of a pair of upper and lower transparent electrodes are patterned (for example, see Non-Patent Document 3).
  • Etc. a partial tilt is applied to the electric field generated between the electrodes, and this makes the liquid crystal alignment multi-domain.
  • This VA mode realizes a display device that can be observed with the same brightness from any angle.
  • Liquid crystal display systems that use ribs are called MVA, ASV, CPA, etc., and those that use both upper and lower transparent electrodes are called PVA.
  • This VA mode is one of the display modes that easily cause color unevenness due to variations in the cell thickness of the liquid crystal cell, and the same tendency may appear in other display modes such as the IPS mode and the CB mode. .
  • Non-Patent Document 1 Akihito Ishikawa Development shortening and mass production application by maskless exposure "," ELECTROTO-TASS mounting technology ", Technical Research Co., Ltd., Vol.18, No.6, 2002, p.74- 79
  • Non-Patent Document 2 Nikkei Microdevices separate volume Flat Panel Display 2003, Practical Edition, pages 82-85, Nikkei BP
  • Non-Patent Document 3 “Nikkei Microdevices separate volume Flat Panel Display 2003”, Practical Edition, page 103, Nikkei BP
  • the present invention has been made to solve the above-described conventional problems, and the present invention cures with high sensitivity even by LDI exposure having a high striking speed and further by LDI exposure which is multiple exposure.
  • the present invention suppresses image distortion due to exposure and fluctuations in the cell thickness of the liquid crystal, enables a high-speed response of display with little display unevenness, and a color filter that can form a high-quality image, and its manufacture Provide a method.
  • the present invention provides a liquid crystal display element that is excellent in responsiveness and can form a high-quality image by employing the color filter of the present invention.
  • R ⁇ R 15 each independently represents a hydrogen atom or a monovalent substituent.
  • the spectral sensitizer (D) is represented by the following general formula (II).
  • A represents an oxygen atom, a sulfur atom or NR 1Q
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 1Q Each independently represents a hydrogen atom or a monovalent substituent
  • R 9 represents a monovalent substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 ,, And R 8 each independently represents a hydrogen atom or a monovalent substituent, and R 9 represents a monovalent substituent.
  • the hydrogen donor (E) is a compound having an acidic proton
  • the photosensitive resin composition for liquid crystal display elements according to ⁇ 1> to ⁇ 5>.
  • the hydrogen donor (E) is a compound having a mercapto group
  • the photosensitive resin composition for liquid crystal display elements according to ⁇ 1> to ⁇ 5>.
  • a photosensitive layer forming step in which a photosensitive resin composition for a liquid crystal display element according to any one of ⁇ 1> to ⁇ 7> is applied to a substrate surface and dried to form a photosensitive resin composition layer And an exposure process for exposing the photosensitive resin composition layer in a pattern at a scanning speed of 5 mm / sec to 3000 m / sec, and a development process for removing uncured areas of the photosensitive layer after exposure.
  • a method for producing a color filter characterized in that
  • thermoplastic resin layer On the temporary support, 1) a thermoplastic resin layer, and 2) any one of ⁇ 1> to ⁇ 7> And a photosensitive layer made of the photosensitive resin composition for a liquid crystal display element.
  • ⁇ 10> ⁇ 9> The photosensitive material for a liquid crystal display element described in ⁇ 9> is laminated on a substrate by contacting the photosensitive layer and the substrate, and the temporary support is peeled off to transfer the photosensitive layer to the substrate surface. Then, the photosensitive layer is exposed in a pattern, and the uncured region of the exposed photosensitive layer is removed.
  • a photosensitive resin composition useful for forming an LCD display element that can be cured with high sensitivity and can form a high-definition image.
  • a color filter having excellent uniformity in pixel and cell thickness, having a high-definition pattern and little display unevenness, and a method for producing the same are provided. can do.
  • the liquid crystal display element of the present invention includes the color filter of the present invention, is capable of high-speed response, and produces a reflex effect when display unevenness is suppressed.
  • FIG. 1 is a perspective view showing an appearance of an exposure unit according to the present invention.
  • FIG. 2 is a perspective view showing a configuration of a scanner of an exposure unit according to the present invention.
  • FIG. 3A is a plan view showing an exposed area formed on a photosensitive material.
  • FIG. 3B is a diagram showing an arrangement of exposure areas by each exposure head.
  • FIG. 4 is a perspective view showing a schematic configuration of an exposure head according to the present invention.
  • 5A is a cross-sectional view in the sub-scanning direction along the optical axis in the configuration of the exposure head shown in FIG.
  • FIG. 5B is a side view in the sub-scanning direction along the optical axis in the configuration of the exposure head shown in FIG. 6] It is a partially enlarged view showing a configuration of a digital micromirror device (DMD).
  • DMD digital micromirror device
  • FIG. 7A is an explanatory diagram for explaining the operation of DMD.
  • FIG. 7B is an explanatory diagram for explaining the operation of the DMD.
  • FIG. 8A is a plan view showing the arrangement of exposure beams and scanning lines in comparison, in which the DMD is not inclined.
  • FIG. 8B is a plan view showing the arrangement of exposure beams and scanning lines in comparison, in which the DMD is arranged in an inclined manner.
  • FIG. 9A is a perspective view showing a configuration of a fiber array light source.
  • FIG. 9B is a partially enlarged view of FIG. 9A.
  • FIG. 9C is a plan view showing an array of light emitting points in the laser emitting portion.
  • FIG. 9D is a plan view showing an array of light emitting points in the laser emitting portion.
  • FIG. 10 is a diagram showing a configuration of a multimode optical fiber.
  • FIG. 12 is a plan view showing a configuration of a laser module.
  • FIG. 13 is a side view showing the configuration of the laser module shown in FIG.
  • FIG. 14 is a partial side view showing the configuration of the laser module shown in FIG.
  • 15A A sectional view showing the depth of focus in the exposure apparatus, where the depth is small.
  • 15B] is a sectional view showing the depth of focus in the exposure apparatus when the depth is large.
  • FIG. 16A is a diagram showing an example of a DMD usage area.
  • FIG. 16B is a diagram showing an example of a DMD usage area.
  • FIG. 17A is a side view showing a proper use area of DMD.
  • FIG. 17B is a cross-sectional view in the auxiliary running direction along the optical axis in FIG. 17A.
  • FIG. 18A is a plan view showing an example of a color filter in the present invention.
  • FIG. 18B is a plan view showing another example of the color filter in the present invention.
  • FIG. 19 is a schematic configuration diagram showing an embodiment of a liquid crystal display device including the color filter of the present invention.
  • the photosensitive resin composition of the present invention comprises (A) a binder, (B) an ethylenically unsaturated compound, (
  • This photosensitive resin composition is a negative photosensitive resin composition, and the photopolymerization initiator (C) is decomposed by exposure to generate an initial species, and the coexisting ethylenically unsaturated compound (B) is polymerized. Proceeds to cause a curing reaction in the exposed area. Therefore, by utilizing the characteristics of this photosensitive resin composition, it is possible to form a high-definition pattern according to the exposure conditions.
  • the photosensitive resin composition for LCD of the present invention contains a photopolymerization initiating lj (C) containing a hexarylbiimidazole compound, and therefore has a wavelength of 350 nm to 420 nm, preferably 390 nm to 420 nm. It is characterized by being cured by exposure.
  • coexistence of the spectral sensitizer (D) with this photopolymerization initiator allows efficient decomposition of the photopolymerization initiator and generation of active species such as radicals, and further functions of the hydrogen donor (E). The radicals generated by this can be efficiently converted into a curing reaction, achieving even higher sensitivity.
  • the photosensitive resin composition of the present invention is required to contain a hexarylbiimidazole compound as a photopolymerization initiator.
  • a hexarylbiimidazole compound as a photopolymerization initiator.
  • Such a compound is represented by the following formula (I). A compound can be mentioned.
  • R ⁇ R 15 each independently represents a hydrogen atom or a monovalent substituent.
  • R ⁇ R 15 in the general formula (I) is more specific. Includes a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a benzyl group, a hydroxyl group, an amino group, a carboxyl group, and the like, among which a hydroxyl group, a halogen atom, an alkyl group, and an alkoxy group are preferable. .
  • Specific examples of the compound represented by the general formula (I) include, for example, a triarylimidazole dimer described in US Pat. No. 3549367, 2, 2′_bis (o —Chlorophen ⁇ 1) 1,4,4 ', 5,5'-tetraphenylbiimidazole, 2,2,1bis (o-chlorophenyl) —4,4', 5,5'-tetra (p-carbo) Ethoxyphenyl) biimidazole, 2,2'-bis (o—black mouth phenyl) 1,4,4 ', 5,5, monotetra (p-bromophenyleno) biimidazole, 2,2'-bis (O_black mouth phenyl) 1, 4, 4 ', 5, 5, one tetra (o, p-dichlorophenyl) biimidazole, etc., among which 2, 2' bis (o_ black mouth) (Phenyl) _4,4 ', 5,5 and
  • the photosensitive resin composition of the present invention is used in combination with a photopolymerization initiator having sensitivity to exposure at the above wavelength other than the hexarylbiimidazole compound within a range not impairing the effect. That power S.
  • Photopolymerization initiators that can be used in combination include aromatic ketones, vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, and US patents. No. 2448828, acyloin ether compounds described in U.S. Pat.No. 27 22512, ⁇ -hydrocarbon substituted aromatic acyloin compounds, U.S. Pat.
  • Preferred examples of the aromatic ketone include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4- Black benzophenone, 4_bromobenzophenone, 2_canolebooxybenzophenone, 2_ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4-methoxy mono 4'-dimethylaminophen Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-tert butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thixanthone, 2-chlorothioxanthone, 2,4 dimethyl Oxanthone,
  • the content of the photopolymerization initiator in the photosensitive resin composition is generally 0.1 to 10% by mass in terms of solid content. 5-5% by mass is preferred.
  • the hexaryl biimidazole compound is based on the content of the total photopolymerization initiator. It is preferably 20 to 80% by mass, especially 30 to 70% by mass Is preferred.
  • a spectral sensitizer (D) suitable for light having a light source wavelength in the range of 350 nm to 420 nm is added. contains.
  • the spectral sensitizer (D) is not particularly limited as long as it has sensitivity in the above wavelength range.
  • One or more compounds selected from compounds represented by the following general formula (II) are preferable.
  • A represents an oxygen atom, a sulfur atom or NR 1Q
  • R 1 , R 2 , R 3 , R ( , R 8 and R 1Q each independently represents a hydrogen atom or a monovalent substituent
  • R 9 represents a monovalent substituent.
  • R 1 , R 2 , R 3 , And R 8 each independently represents a hydrogen atom or a monovalent substituent, and R 9 represents a monovalent substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 examples of the monovalent substituent represented by R 8 include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a trifluoromethyl group, a benzyl group, a sulfopropyl group, a jetyl group).
  • alkylthio groups or arylthio groups for example, methylthio groups, carboxyethylthio groups, sulfobutylthio groups, phenylthio groups, etc.
  • alkoxy groups carbonyl groups for example, methoxycarbonyl groups
  • Examples include a aryloxycarbonyl group (for example, a phenoxycarbonyl group).
  • the monovalent substituents represented by R 5 , R 6 , R 7 and R 8 may further have a substituent.
  • substituents include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a trifunoleolomethinole group, a benzyl group, a sulfopropyl group, a jetylaminoethyl group, a cyanopropyl group.
  • benzenesulfonyl group Suruhoniruamino group ( For example, methanesulfonylamino group, benzenesulfonylamino group, etc.), amino group (eg, jetylamino group, hydroxyamino group, etc.), alkylthio group or arylthio group (eg, methylthio group, carboxyethylthio group, sulfo group) Butylthio group, phenylthio group and the like), alkoxycarbonyl group (for example, methoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group and the like) and the like.
  • amino group eg, jetylamino group, hydroxyamino group, etc.
  • alkylthio group or arylthio group eg, methylthio group, carboxyethylthio group, sulfo group
  • R 8 may be linked together by a saturated straight chain, saturated branched chain, unsaturated straight chain, unsaturated branched chain, etc. to form a ring structure, and they may further contain the above substituents. Have it, get it,
  • the monovalent substituent represented by R 9 includes an alkyl group, an aryleno group, an alkenyl group, an alkoxy group, an aryloxy group, an acyl group,
  • An alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxycarbonyl group are preferable, and an alkyl group, an aryleno group, an alkenyl group, and an acyl group are particularly preferable.
  • the alkyl group preferred by the alkyl group is 1 to: 12 is preferred, and 1 to 6 is more preferred.
  • These monovalent substituents represented by R 9 may further have a substituent.
  • substituents include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxychetyl group, a trifunoleolomethylol group, a benzyl group, a sulfopropyl group, a jetylaminoethyl group, a cyanopropyl group, an adamantyl group P-chlorophenethyl group, ethoxyethynole group, ethylthioethyl group, phenoxycetyl group, strong rubamoylethyl group, carboxycetyl group, ethoxycarbonylmethyl group, acetylethylaminoethyl group, etc.), alkenyl group (for example, arryl group, styryl group, etc.
  • R 9 is R 1 R 2 , R 3 ,
  • R 8 may be linked to a saturated straight chain, a saturated branched chain, an unsaturated straight chain, an unsaturated branched chain, or the like, or they may have the above-mentioned substituent.
  • the monovalent substituent represented by R 1Q in the definition of A includes an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group, an alkyl group.
  • An alkyl group, alkoxy group, aryloxy group, acylol group, alkylthio group, and alkoxycarbonyl group are particularly preferred, which are preferably a nolealkylthio group, an aryloxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • the Yogu the substituent may have a substituent further monovalent substituent represented by these R 1Q, an alkyl group (e.g., methyl group, Echiru group, propyl group, butyl group , Hydroxychetyl group, trifnoleolomethinole group, benzyl group, sulfopropyl group, decylaminoethyl group, cyanopyl group, adamantyl group, p-chlorophenethyl group, ethoxyethynole group, ethylthioethyl group, phenoxycetyl group, rubamoylethyl group, Carboxycetyl group, ethoxycarbonylmethyl group, acetylylaminoethyl group, etc.), alkenyl group (eg, aryl group, styryl group, etc.), aryl group (eg, phenyl group, nap
  • Halogen atom eg, chlorine atom, bromine atom, fluorine atom, etc.
  • mercapto group cyano group, carboxyl group, sulfo group, hydroxy group, force rubamoyl group, sulfamoyl group, nitrile group, alkoxy group (eg, methoxy group, Ethoxy group, 2-methoxyethoxy group, 2_phenylethoxy group, etc.), aryl-oxy group (for example, phenoxy group, p_methylphenoxy group, p-chlorophenoxy group, ⁇ -naphthoxy group, etc.), isyl group (for example, , Acetyl groups, benzoyl groups, etc.), acylamino groups (eg, acetylenoamino groups, force-propylamine groups, etc.), sulfonyl groups (eg, methanesulfonyl groups, benzenesulfonyl
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 9 may be linked to a saturated straight chain, a saturated branched chain, an unsaturated straight chain, an unsaturated branched chain, or the like, or they may have the above-mentioned substituent.
  • the content of the spectral sensitizer (D) in the photosensitive resin composition is preferably 0.5 to 3% by mass in terms of solid content. 1.0 to 2.0 More preferably, it is mass%.
  • the hydrogen donor ( ⁇ ) used in the present invention is not particularly limited as long as it is a compound that can donate a hydrogen atom to a radical generated by the decomposition of the polymerization initiator (C). Generally, an acidic proton is used. The compound which has is used. Such a compound has a function as a chain transfer agent and is known to be useful for promoting radical polymerization.
  • a known compound having this function can be used as the hydrogen donor ( ⁇ ) in the present invention, and examples thereof include amine compounds and mercapto compounds. Among them, compounds having a mercapto group are used. Les, I prefer to be.
  • I ⁇ represents an alkyl group or an aryl group
  • b represents a hydrogen atom or an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group.
  • this aryl group may be substituted. Examples of such a substituted aryl group include the above-described aryl group, a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, a methoxy group, and an ethoxy group. Those substituted with an alkoxy group such as a group are included.
  • R 25 and R 26 may be bonded to each other to form a heterocyclic ring with a carbon atom and a nitrogen atom, and this heterocyclic ring may have a condensed ring.
  • the condensed ring include a benzene ring.
  • Phenol 2 Mercapto 1—Methyl, Resulfonyl-1, 3 Benzimidazo
  • Examples of hydrogen donors having two mercapto groups in one molecule include 1,2-ethanedithionore, 1,3-propanedithionore, 1,4-butanedithionore, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octane dithionore, 1,9-nonandiothiole, 2,3-dimenorecapto 1-propanole, dithioerythritol, 2,3-di Mercaptosuccinic acid, 1,2_benzenedithiol, 1, 2 —benzenedimethanethiol, 1,3_benzenedithiol, 1,3_benzenedimethanethiol, 1,4_benzenedimethanethiol, 3,4-di Mercaptotoluene, 4_ black mouth 1, 3 Benzene Dithionore, 2, 4, 6 Trimethinore 1, 3 Benzene Dime
  • Examples of hydrogen donors having three mercapto groups in one molecule include 1, 2, 6_ hexanetri-noretritian glycolate, 1, 3, 5 tritium diananoic acid, 2, 4, 6 trimenole.
  • Examples include capto 1,3,5-triazine, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trismercaptoacetate, and the like.
  • Examples of the compound having four or more mercapto groups in one molecule include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakismenolecaptoacetate, dipentaerythritol hexakis (3-mercaptopro Pionate) and dipentaerythritol hexakismercaptoacetate.
  • These hydrogen donors (E) may be used alone or in combination of two or more.
  • the content of the hydrogen donor (E) in the photosensitive resin composition is preferably 0.05 to 5.0 mass% in terms of solid content. More preferably, it is mass%.
  • the binder (A) contained in the photosensitive resin composition functions as a film-forming substance when a layer made of the photosensitive resin composition is formed on the surface of the base material.
  • the binder (A) is preferably an ethylenically unsaturated compound (B) described later, in which the polymer compound used as the binder (A) preferably has a crosslinkable group or a polymerizable group.
  • the crosslinking density in the photosensitive resin composition is preferably selected under the condition that it can be set to 0.0073 mol / g or more.
  • the polymer compound constituting the binder preferably has a crosslinking group as described above.
  • the polymer compound is appropriately selected according to the purpose and used, and may be any of a monomer homopolymer and a copolymer composed of a plurality of monomers. Examples of such a polymer compound include a structural unit having a carboxyl group, a structural unit represented by the following general formula (1), and a (meth) atrelate having one or more aromatic rings and Z or aliphatic rings. A copolymer having at least a structural unit is preferable.
  • This copolymer includes, for example, a polymerizable monomer having a carboxynole group, a monomer represented by the following formula (2), a (meth) acrylate having one or more aromatic rings and / or aliphatic rings, If necessary, other monomers copolymerizable with these can be obtained by a known copolymerization method.
  • R 1 represents a hydrogen atom or a methyl group
  • R 6 may independently have a hydrogen atom or a substituent. It represents an alkyl group, an aryl group, a halogen atom or a cyan group.
  • Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride can also be used.
  • An anhydride monomer such as maleic anhydride and itaconic anhydride can also be used as a precursor of carboxylic acid.
  • (meth) acrylic acid is particularly preferable from the viewpoint of polymerizability and raw material price.
  • Examples of the monomer represented by the formula (2) include, for example, aranole (meth) acrylate, 3-chloro 1-propenyl (meth) acrylate, 3-phenol 2-propene. Nil (meta) attareido 3-(Hydroxyphenyl) 1-2 propenyl (meth) acrylate, 3-(2 hydroxy phenyl) 2 propenyl (meth) acrylate, 3-(3, 4 dihydroxy phenyl) 1—Propenyl (meth) atarylate, 3-(2,4-dihydroxyphenyl) -2 Propenyl (meth) acrylate, 3— (3, 4, 5, Trihydroxyphenyl ) 1-propenyl (meth) acrylate, 3 _ (3-methoxy 4-hydroxyphenyl) _ 2 _propenyl (meth) acrylate, 3- (3, 4-dihydroxy _ 5— Methoxyphenyl) _ 2_propenyl (meth) acrylate,
  • aryl (meth) acrylate is particularly preferred in terms of curability and raw material price.
  • the "(meth) acrylate having at least one aromatic ring and / or aliphatic ring” includes, for example, (meth) acrylic acid cycloalkyl ester [for example, (meth) acrylic acid cyclohexenole, (Meth) norbornyl acrylate, (Mad) adamantyl acrylate, etc.], (Meth) Atari Aryl ester [for example, (meth) acrylic acid phenyl, (meth) acrylic acid chlorophenyl, (meth) acrylic acid methoxyphenyl, (meth) acrylic acid naphthyl, etc.], aralkyl ester [for example, (meth) acrylic Benzyl acid, phenethyl (meth) acrylate, etc.].
  • (meth) acrylic acid cycloalkyl ester for example, (meth) acrylic acid cyclohexenole, (Meth) norbornyl acrylate, (Mad) adamant
  • (meth) acrylic acid benzenole and (meth) acrylic acid cyclohexyl are preferred in terms of raw material price, solubility, pigment dispersibility, and the like.
  • (meth) acrylic acid alkyl ester for example, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid n_butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid t-butyl, (meth) acrylic acid hexyl, (meth) acrylic (Meth) acrylic acid ( ⁇ O 18 ) alkyl esters such as octyl acid, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.];
  • (Meth) acrylic acid aralkyl esters [eg (meth) acrylic acid benzyl, etc.], substituted (meth) acrylic acid alkyl esters [eg, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate , Dimethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.], (meth) acrylamides [eg (meth) alkyl
  • Method acrylic acid alkyl ester for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropylene (meth) acrylate, (meth) N-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-methylhexyl (meth) acrylate Etc.] are particularly preferred.
  • the copolymerization ratio of each component is 1 0-40 Monore 0/0 Ca preferably "structural unit having a carboxyl group", 15-35 Monore 0/0 Ca More preferably, 20 to 35 Monore 0 / 0 force S is particularly preferable.
  • the structural unit having a carboxynole group is within the above range, good developability is obtained and the developer resistance of the image area is also good.
  • it or 20-80 Monore 0/0 force S preferably "Concrete unit structure represented by the general formula (1)", 20-75 Monore 0/0 force S, and particularly preferably 25 to 75 Monore%.
  • the structural unit represented by the general formula (1) is within the above range, good curability and developability can be obtained.
  • the structural unit composed of (meth) acrylate having at least one aromatic ring and / or aliphatic ring is within the above range, the pigment dispersibility is excellent and the developability and curability are also good.
  • the weight average molecular weight of the copolymer suitable as a binder is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 80,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of the suitability for producing the copolymer and the developability.
  • the copolymer suitable as the binder ( ⁇ ) can be obtained by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be obtained by dissolving these monomers in a suitable solvent, adding a radical polymerization initiator to this solution and polymerizing them in the solution.
  • An appropriate solvent for copolymerization can be arbitrarily selected depending on the solubility of the monomer and the copolymer to be produced.
  • solvents include, for example, methanol, ethanol, Examples include propanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chlorophenol, toluene, and mixtures thereof.
  • a polymerization initiator can be used.
  • polymerization initiator examples include 2, 2′-azobis (isobutyronitrile) (AIBN), 2, 2′-azobis mono (2, 4′— Azo compounds such as dimethylvaleronitrile), peroxide compounds such as benzoyl peroxide, and persulfates can be used.
  • AIBN 2, 2′-azobis (isobutyronitrile)
  • 2, 2′-azobis mono (2, 4′— Azo compounds such as dimethylvaleronitrile
  • peroxide compounds such as benzoyl peroxide
  • persulfates examples include 2, 2′-azobis (isobutyronitrile) (AIBN), 2, 2′-azobis mono (2, 4′— Azo compounds such as dimethylvaleronitrile), peroxide compounds such as benzoyl peroxide, and persulfates can be used.
  • a known chain transfer agent may be appropriately used for the purpose of adjusting the molecular weight. Furthermore, if necessary, the polymerization concentration, initiator amount, chain transfer agent, polymerization temperature, etc. are adjusted appropriately. For example, the polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
  • the content of the binder (A) in the photosensitive resin composition is preferably 30 to 70% by mass, preferably 40 to 50% by mass in terms of solid content.
  • ethylenically unsaturated compound (B) those having a crosslinking group are preferable, and any compound having at least one addition-polymerizable ethylenically unsaturated group is not particularly limited and may be used depending on the purpose. It can be selected appropriately.
  • examples of the ethylenically unsaturated compound (B) include ester compounds, amide compounds, and other compounds.
  • examples of the ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, and isocrotonic acid ester. , Maleic acid esters, other ester compounds, and the like. These ester compounds may be used alone or in combination of two or more. Of these, monofunctional (meth) acrylic acid esters and polyfunctional (meth) acrylic acid esters are preferred.
  • Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono
  • Examples of the polyfunctional (meth) acrylic acid ester include polyethylene glycol di (meth) ) Atallate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, hexane Diol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Rutetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta erythritolorepoly (meth) acrylate, sonorebitonoretri
  • polyfunctional (meth) acrylic acid ester examples include those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 Urethane Atylates, Japanese Patent Publication No. 48-64183, Japanese Publication No. 49 43191 And polyester acrylates described in JP-B-52-30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, JP-A-60-258539 Examples thereof include (meth) acrylic acid esters, urethane (meth) acrylates, and vinyl esters described in the publication.
  • ester compounds cited as examples of the ethylenically unsaturated compound (B) examples include trimethylolpropane tri (atalylooxypropyl) ether, tri (atariloy mouth chechtil) Examples include isocyanurate, photocurable monomers and oligomers described in Japan Adhesive Association Vol. 20, No. 7, pp. 300-308, and the like.
  • examples of the amide compound include an amide (monomer) of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound.
  • Specific examples of amide compounds include methylene bis (meth) atalinoleamide, 1,6_hexamethylene bis (meth) acrylamide, and diethylenetriamine tris (meth) acrylamide. , Xylylenebis (meth) acrylamide, and the like.
  • (meth) acrylic acid amides described in JP-A-60-258539 are also examples of the amide compounds.
  • examples of the "other compounds” include aryl compounds described in JP-A-60-258539.
  • the ethylenically unsaturated compound (B) may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound (B) in the photosensitive resin composition is preferably 10 to 60% by mass with respect to the total solid content of the photosensitive resin composition or the photosensitive resin composition layer. More preferably, it is 20 to 50% by mass.
  • the content of the binder (A) in the photosensitive resin composition is the content of the binder (A) in the photosensitive resin composition
  • the ratio of (% by mass) to the content (% by mass) of the ethylenically unsaturated compound (B) is preferably ⁇ or 0.6 to 1.5, more preferably ⁇ or 0.7 to 1.0. It is.
  • the photosensitive resin composition of the present invention may further include a colorant, a surfactant, a solvent, a thermal polymerization inhibitor, an ultraviolet absorber, and the like as necessary.
  • a colorant e.g., a terephthalate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate
  • colorant examples include dyes and pigments. This colorant is used as necessary for the member of the color filter formed by the photosensitive resin composition.
  • the preferred pigment type, size, and the like can be appropriately selected from, for example, the description of Japanese Patent Application Laid-Open No. 11-149008.
  • a colorant such as a pigment
  • a colored pixel can be formed.
  • usable pigments include extender pigments and colored pigments.
  • the extender pigment is not particularly limited and can be appropriately selected according to the purpose.
  • extender pigments described in paragraphs [0035] to [0041] of Japanese Patent Application Laid-Open No. 2003-302 639 are preferable.
  • the coloring pigment a pigment described in paragraph number [0043] of Japanese Patent Application Laid-Open No. 2003-302639 is preferably used.
  • any surfactant can be used as long as it is mixed with the constituent components of the photosensitive resin composition (or photosensitive layer).
  • preferable surfactants paragraph numbers [0015] to [0024] of JP-A-2003-337424, paragraph numbers [0012] to [0017] of JP-A-2003-177522, Paragraph Nos. [0012] to [0015] of Japanese Patent Publication No. 2003-177523, Paragraph Nos. [0010] of Japanese Patent Publication No. 2003-177521, Paragraph Nos. [0010] of Japanese Patent Publication No. 2003_177519 [0013], paragraph numbers [0012] to [0015] of Japanese Unexamined Patent Publication No.
  • fluorosurfactant and / or a silicon surfactant fluorine surfactant or silicon surfactant, containing both fluorine atom and silicon atom
  • fluorosurfactants in which it is preferable to select one or more of the above.
  • the fluorine-containing substituent in the surfactant molecule preferably has 1 to 38 fluorine atoms, more preferably 5 to 25 fluorine atoms 7 to 20 Most preferred. It is desirable for the number of fluorine atoms to be in the above-mentioned range because solubility is good and unevenness is improved.
  • a particularly preferred surfactant includes a monomer A represented by the following general formula (a) and a monomer B represented by the following general formula (b) as copolymerization components.
  • the surfactant include a copolymer having a copolymerization ratio ([mass ratio]) force of 20/80 to 60/40 between the monomer A and the monomer B (hereinafter referred to as “surfactant suitable for the present invention”). Also referred to as an “agent”).
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom or a methyl group, preferably R 2 is a hydrogen atom, and R 3 is a methyl group.
  • R 4 represents a hydrogen atom or an alkyl group having from! Examples of the alkyl group represented by R 4 include a methyl group, an ethyl group, a propyl group, a butyl group, and the like, and among them, a methyl group or an ethyl group is preferable. R 4 is particularly preferably a hydrogen atom.
  • n represents an integer of 1 to 18 and preferably an integer of 2 to 10: m represents an integer of 2 to: 14, preferably an integer of 4 to 12.
  • C F in the general formula (a) is
  • p and q each independently represent an integer of 0 to 18 and preferably 2
  • the plurality of monomers A contained in one molecule may have the same structure or different structures, and the same applies to the monomer B. is there.
  • Suitable surfactants in the present invention (copolymer), based on the total weight of the copolymer, wherein 20 to 60 mass Monomer A 0/0, the monomer B and 80 to 40 mass 0 / 0, and the other optional monomer other than monomers a and B to the remaining mass% and the copolymerization ratio is preferably tool further includes a monomer a 25 to 60 weight 0/0, 60 monomers B 40 mass 0/0, and the monomer a and from 25 to 60 mass than other copolymerizable ratio as its remaining mass% of any monomer a Konomashigumo Nomar a B 0/0, 75 to the monomer B 40 mass 0/0, and copolymerization ratio of the other optional monomer other than said monomers a and B and the rest of mass% is more preferable.
  • R 1 in the general formula (a) is a hydrogen atom
  • R 3 is a methyl group
  • P 0
  • organic solvent can also be used for the preparation of the photosensitive resin composition of the present invention.
  • organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol nole mono methinoate ethere acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactyl lactate, methyl lactate, strength prolatatum, etc. It is possible to raise S.
  • the photosensitive resin composition of the present invention can further contain a thermal polymerization inhibitor.
  • thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t butinole, p-crezo-no-re, pyrogalonore, t-butinore force, teconole, benzoquinone, 4, 4'-thiobis (3 -Methyl 6-t butylphenol), 2,2'-methylenebis (4-methyl-6-t butylphenol), 2 mercaptobenzimidazole, phenothiazine and the like.
  • the photosensitive resin composition of this invention can contain a ultraviolet absorber as needed.
  • a ultraviolet absorber examples include compounds described in Japanese Patent Laid-Open No. 5-72724, salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, hindered amines, and the like.
  • UV absorber examples include phenyl salicylate, 4_t-butylphenyl salicylate, 2,4-di_t_butylphenyl_3 ', 5'_di-t_4'-hydroxy Benzoate, 4 t-butylphenyl salicylate, 2, 4 dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 n-otatoxiben zophenone, 2- (2'-hydroxy 1-5'-methylphenyl) benzo Triazole, 2— (2′—Hydroxy 1 3 ′ _t_Butyl _ 5 ′ _Methylphenyl) _ 5 _Cloguchibenzotriazole, Ethyl 1 _Ciano _ 3,3-Diphenyl atylate, 2, 2 ′ —Hydroxy _4 methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,
  • the photosensitive resin composition of the present invention may contain "adhesion aid" described in Japanese Patent Application Laid-Open No. 11-133360, other additives, and the like in addition to the additives. .
  • the photosensitive resin composition for a liquid crystal display element of the present invention is applied to the surface of a substrate and dried to form a photosensitive resin composition layer (hereinafter referred to as a sensitive film). And a step of exposing the photosensitive layer in a pattern, and a step of removing and developing an uncured region of the photosensitive layer after the exposure.
  • a coating method liquid registration method
  • the second aspect of the color filter manufacturing method is a method using a transfer material using the photosensitive resin composition for liquid crystal display elements. That is, in the second embodiment, 1) a thermoplastic resin layer and 2) a photosensitive layer made of the photosensitive resin composition for a liquid crystal display element of the present invention are laminated in this order on a temporary support.
  • the photosensitive material for a liquid crystal display element is used, the surface opposite to the temporary support is brought into contact with the base material, the workable material is laminated on the base material, the temporary support is peeled off, and the base material is peeled off.
  • the photosensitive layer is patterned. It is characterized by exposing and removing an uncured region of the photosensitive layer after exposure (development process).
  • the second embodiment of this production method will be referred to as a transfer method as appropriate.
  • the exposure step and the development step performed after forming the photosensitive layer are the same steps as in the first embodiment.
  • the photosensitive resin composition for a liquid crystal display element of the present invention is dissolved or dispersed in an appropriate liquid to prepare a coating solution, which is applied to the substrate surface and dried.
  • a photosensitive layer is formed.
  • the solvent or dispersant can be appropriately selected from known liquids such as water or organic solvents, depending on the composition of the photosensitive resin composition.
  • the method for applying the coating solution to the surface of the substrate for example, spin coating, curtain coating, slit coating, dip coating, air knife coating, roller, and the like.
  • a coating method, a wire bar coating method, a gravure coating method, an etching coating method using a popper described in US Pat. No. 2681294, or the like can be selected and applied according to the purpose.
  • a method using a slit coater provided with a slit-shaped nozzle having a slit-like hole in the discharge portion of the coating liquid is preferable.
  • Japanese Patent Laid-Open No. 2004-89851 Japanese Patent Laid-Open No. 2004-17043, Japanese Patent Laid-Open No. 2003-170098, Japanese Patent Laid-Open No. 2003-164787
  • the slit-shaped nozzle and slit coater described in Japanese Patent Laid-Open No. 2003-10767, Japanese Patent Laid-Open No. 2002-79163, Japanese Patent Laid-Open No. 2001-310147, etc. are preferably used.
  • drying the coating film containing the photosensitive resin composition coated on the substrate a known method can be appropriately used.
  • the drying conditions vary depending on the formulation of the photosensitive resin composition used and the type of solvent, but generally a temperature range of 70 to 150 ° C is preferred.
  • the layer thickness is preferably in the range of 0.5 to 10 ⁇ m, more preferably in the range of 1 to 6 zm.
  • the layer thickness is in the above range, Generation of pinholes during application is prevented, and development and removal of the unexposed area can be performed within an appropriate time without affecting the exposed and cured areas.
  • another layer may be provided on the surface of the base material depending on the purpose of coating the photosensitive resin composition to form a photosensitive layer.
  • Other optional layers include a protective layer having an oxygen barrier property for suppressing polymerization inhibition by oxygen during the curing reaction of the photosensitive layer, an adhesive layer for improving the adhesion between layers, and a desired region.
  • a light blocking layer that suppresses the light transmittance to the light.
  • a photosensitive material for a liquid crystal display element produced using the photosensitive resin composition for a liquid crystal display element of the present invention is used.
  • This photosensitive material for liquid crystal display elements functions as a photosensitive transfer material.
  • the structure can be suitably formed by using an integral transfer film such as a resin transfer material described in JP-A-5-72724. Examples of the constitution of the integral transfer photosensitive material include: 1) a thermoplastic resin layer and optionally an intermediate layer on a temporary support; and 2) a photosensitive resin composition for a liquid crystal display device of the present invention.
  • a laminated structure in which a photosensitive layer made of a product and a protective layer if desired is provided is preferred.
  • the photosensitive layer in the photosensitive material is a layer composed of the photosensitive resin composition of the present invention.
  • a photosensitive coating solution obtained by dissolving or dispersing the photosensitive resin composition of the present invention in an appropriate solvent is known. It can be suitably formed by coating and drying by a coating method.
  • a known application method can be appropriately used.
  • a coating method by slit-shaped nozzle having a slit-shaped hole in the discharge portion of the coating liquid is preferable. Slit nozzle and slit coater The details of are as described above.
  • the thickness of the photosensitive layer in the photosensitive material is preferably 0.5 to: ⁇ ⁇ ⁇ force S, more preferably than! To 6 / im force S, for the same reason as described in the coating method. Masle.
  • thermoplastic resin layer One thermoplastic resin layer
  • the photosensitive material of the present invention has at least one thermoplastic resin layer between the photosensitive layer and the temporary support.
  • thermoplastic resin layer has a function as a cushioning material that effectively prevents transfer failure caused by unevenness on the transfer material when the photosensitive layer is transferred to the transfer material. . Therefore, the thermoplastic resin layer can be deformed in accordance with the unevenness on the transfer material when the photosensitive transfer material is heat-pressed to the transfer material, thereby improving the adhesion between the photosensitive layer and the transfer material. I can power.
  • thermoplastic resin layer is removed together with an unnecessary (uncured) photosensitive layer by development after transfer, it is preferable to use a thermoplastic resin capable of alkali development.
  • thermoplastic resin capable of alkali development.
  • alkali-soluble resin from the viewpoint of suppressing the contamination of the transferred material by the thermoplastic resin layer protruding during transfer.
  • the layer thickness of the thermoplastic resin layer in the light-sensitive material of the present invention is preferably from 0.:! To 20 ⁇ .
  • the layer thickness is more preferably 1.5 to 16 ⁇ , and most preferably 5 to 15. O / im.
  • the reticulation refers to the fact that when the intermediate layer is stretched due to moisture absorption or the like, the soft cushion layer is buckled and fine "wrinkles" are generated on the surface of the photosensitive layer. This may cause poor transfer.
  • the thermoplastic resin layer can be composed of at least a thermoplastic resin, and other components can be appropriately used as necessary.
  • the thermoplastic resin is not particularly limited as long as it has alkali solubility, and can be appropriately selected. Those having a substantial softening point of 80 ° C or less are preferred.
  • thermoplastic resin having a substantial softening point of 80 ° C or lower examples include, for example, ethylene and alcohol.
  • Preferable examples include esters, and canes such as (meth) acrylate copolymers of butyl (meth) acrylate and vinyl acetate.
  • the soft spot described in “Plastic Performance Handbook” is approximately 80 ° C or less.
  • the organic polymers those soluble in alkali are also included. These may be used alone or in combination of two or more.
  • the substantial softening point is 80 ° C or lower, and even if it is an organic polymeric material itself having a softening point of 80 ° C or higher, it is compatible with the organic polymeric material.
  • the plasticizer is not particularly limited and can be appropriately selected according to the purpose. Examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, talezyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.
  • the alkali-soluble thermoplastic resin layer has a substantial softening point of more than 80 ° C for the purpose of adjusting the adhesive force with the temporary support as another component.
  • Various polymers, supercooling substances, adhesion improvers, surfactants, mold release agents, and the like can be added within the range.
  • the photosensitive transfer material is preferably provided with an intermediate layer for the purpose of preventing mixing of each component when applying a plurality of layers and during storage after application.
  • an intermediate layer for the purpose of preventing mixing of each component when applying a plurality of layers and during storage after application.
  • it is preferably provided between the thermoplastic resin layer provided on the temporary support and the photosensitive layer.
  • An organic solvent is used to form the thermoplastic resin layer and the photosensitive layer.
  • mixing due to the compatibility of the two layers in contact with P can be prevented when the photosensitive layer is applied.
  • the component used in the intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.
  • Known constituent materials can be used for the intermediate layer.
  • polybutyl ether described in Japanese Patent Application Laid-Open No. 46-2121 and Japanese Patent Publication No.
  • Water maleic acid polymer water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ether, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, water-soluble polyamide, water-soluble salt of polyacrylic acid , Gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and the like. These components may be used alone or in combination of two or more.
  • a water-soluble resin that is, a water-soluble polymer material.
  • a water-soluble polymer material at least, it is more preferable to use polybutyl alcohol, and polyvinyl alcohol and polybutylpyrrolidone. Is particularly preferable.
  • the polybulal alcohol is not particularly limited and can be appropriately selected according to the purpose, and those having a hatching degree of 80 mol% or more are preferred.
  • ⁇ 75% by volume is preferred:! ⁇ 60% by volume is more preferred 10 ⁇ 50% by volume is particularly preferred.
  • the content of polyvinyl pyrrolidone is within the above range, sufficient adhesion with the thermoplastic resin layer can be obtained, and the oxygen blocking ability is also good.
  • the intermediate layer preferably has a low oxygen permeability. That is, it is preferable to be composed of an oxygen blocking film having an oxygen blocking function. As a result, the sensitivity at the time of exposure is increased, the time load of the exposure machine can be reduced, the productivity can be improved, and the resolution can be improved.
  • the thickness of the intermediate layer is preferably about 0.:! To about 5 ⁇ , more preferably about 0.5 to 2 ⁇ m.
  • the oxygen barrier property is not lowered, and it is possible to prevent the intermediate layer removal time during development from increasing.
  • thermoplastic resin layer As the temporary support, a material that is chemically and thermally stable and flexible is preferable to have a peelability from the thermoplastic resin layer to the extent that does not hinder the transfer.
  • the material of the temporary support is not particularly limited, and can be appropriately selected depending on the purpose.
  • Examples of the temporary support include polytetrafluoroethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and polypropylene. I can get lost.
  • the structure of the temporary support is not particularly limited and may be appropriately selected depending on the purpose, and may be either a single-layer structure or a laminated structure.
  • the temporary support also has an undercoat layer such as gelatin, which is preferably not subjected to surface treatment such as glow discharge from the viewpoint of ensuring good releasability with the thermoplastic resin layer. It is preferable not to provide it.
  • the thickness of the temporary support is preferably about 5 to 300 111, and more preferably 20 to 150 ⁇ m force.
  • the temporary support preferably has a conductive layer on at least one surface thereof, or the temporary support itself has conductivity.
  • the temporary support is removed when the temporary support is peeled off after the photosensitive transfer material provided with the temporary support is brought into close contact with the transfer target. N
  • the transferred material is not charged and attracts surrounding dust.
  • dust or the like does not adhere to the thermoplastic resin layer, and the formation of pinholes associated with the formation of extra unexposed portions in the subsequent exposure process is effectively achieved. Can be prevented.
  • the surface electrical resistance on the surface of the conductive layer on the temporary support or the temporary support having conductivity is preferably 10 13 ⁇ or less.
  • the temporary support having conductivity is obtained by containing a conductive substance in the temporary support.
  • the conductive substance is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include metal oxides and antistatic agents.
  • Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide. These may be used alone or in combination of two or more. Examples of the metal oxide include crystal fine particles and composite fine particles.
  • Examples of the antistatic agent include alkyl phosphate anionic surfactants such as Electro Stripper Sakai (manufactured by Kao Corporation), Elenon No. 19 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Betaine amphoteric surfactants such as Ichigen K (Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene fatty acid ester nonionic surfactants such as Nissan Nonion L (Nippon Yushi Co., Ltd.), Emanoregen 106, Polyoxyethylene alkyl ether type nonionic surfactants such as 120, 147, 420, 220, 905, 910 (made by Kao Corporation) and Nissan Nonion E (made by NOF Corporation), Polyoxyethylene alkyl phenol ether, polyvalent al Examples thereof include other nonionic surfactants such as a cholic fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, and a poly
  • the conductive layer can be formed by appropriately selecting from a configuration using a known conductive substance.
  • a known conductive substance For example, ZnO, TiO, SnO, AlO, InO, SiO, MgO, BaO, Mo can be used as the conductive material in that a stable conductive effect can be obtained without being affected by the humidity environment.
  • O and the like are preferable. These may be used alone or in combination of two or more.
  • the volume resistance value of the metal oxide or the conductive substance is preferably 10 7 Q′cm or less, and more preferably 10 5 ⁇ ′cm or less. Further, the particle diameter of the metal oxide or the conductive substance is preferably 0.01 to 0.7 zm, more preferably 0.02 to 0.5 ⁇ m.
  • cellulose for example, cellulose, cellulose ester such as gelatin, cellulose nitrate, cenorelose triacetate, cenorelose diacetate, cenorelose acetate butyrate, cellulose acetate propionate, vinylidene chloride, chloride Homopolymers or copolymers, such as biels, styrene, atarylnitrinoles, vinyl acetate, alkyl acrylates having 1 to 4 carbon atoms, bilipyrrolidone, etc., soluble polyesters, polycarbonates, soluble polyamides, etc. can be used.
  • cellulose cellulose ester
  • cenorelose triacetate cenorelose diacetate
  • cenorelose acetate butyrate cellulose acetate propionate
  • vinylidene chloride chloride
  • Homopolymers or copolymers such as biels, styrene, atarylnitrinoles, vinyl a
  • the photosensitive transfer material can be further provided with a protective film or the like as another layer.
  • the protective film has a function of protecting the photosensitive layer from dirt and damage during storage and the like, and can be composed of the same or similar material as the temporary support.
  • As the protective film it is sufficient if the light-sensitive layer strength can be easily peeled off.
  • silicon paper, polyolefin sheet, polytetrafluoroethylene sheet and the like are preferably used. Among these, a polyethylene sheet or film, a polypropylene sheet or film are preferred.
  • the film thickness of the protective film is preferably about 5 to about 100 ⁇ m, more preferably 10 to 30 ⁇ .
  • the photosensitive transfer material in the present invention is obtained by applying a solution (thermoplastic resin coating solution) in which an additive is dissolved together with a thermoplastic organic polymer (thermoplastic resin) onto a temporary support. After drying and providing a thermoplastic resin layer, if necessary, a prepared liquid (intermediate solution) prepared by adding a resin or additive to a solvent that does not dissolve the thermoplastic resin layer on this thermoplastic resin layer.
  • the photosensitive resin composition was prepared as described above by coating the coating liquid for the layer), drying and laminating the intermediate layer, and further dissolving the intermediate layer on the intermediate layer and using the solvent. It can be suitably produced by applying a product, drying it and laminating a photosensitive layer.
  • the photosensitive transfer material of the present invention has a first sheet in which a thermoplastic resin layer and an intermediate layer are provided in this order from the temporary support side on the temporary support, and a photosensitive layer on the protective film. Two sheets can be prepared and bonded so that the surface of the intermediate layer of the first sheet is in contact with the surface of the photosensitive layer. Furthermore, the photosensitive transfer material in the present invention is a first sheet in which a thermoplastic resin layer is provided on a temporary support, and a second sheet in which a photosensitive layer and an intermediate layer are provided in this order from the protective film side on a protective film. It is also possible to prepare the sheet by laminating it so that the surface of the intermediate layer of the second sheet is in contact with the surface of the thermoplastic resin layer of the first sheet.
  • the photosensitive layer forming step by the transfer method comprises laminating a photosensitive material for a liquid crystal display element on a substrate in contact with a surface opposite to the temporary support and the temporary support. This is a process of peeling and transferring the photosensitive layer to the substrate surface.
  • the protective film is peeled off, and the exposed surface of the photosensitive layer is transferred to the substrate surface as a transfer material.
  • the substrates are bonded together by pressure bonding or heat pressure bonding with a heated and / or pressurized roller or flat plate, and then the temporary support is peeled off to transfer the photosensitive layer onto the substrate. Bonding can be suitably performed using a known laminator (vacuum laminator or the like), and an auto cut laminator is preferable from the viewpoint of increasing productivity.
  • the layer thickness when the photosensitive layer is formed by the transfer method is the same as that by the coating method. This Since the film thickness is determined when a photosensitive material for transfer is prepared, it may be formed with a desired film thickness when the photosensitive layer made of the photosensitive resin composition is formed.
  • the substrate used for forming the photosensitive layer for example, a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), or a substrate with a color filter (also referred to as a color filter substrate). ), A driving substrate with a driving element (for example, a thin film transistor [TFT]), and the like.
  • the thickness of the substrate is appropriately selected according to the purpose of use of the color filter, but generally it is preferably in the range of 700 to: ⁇ 200 ⁇ .
  • the substrate can be subjected to a coupling treatment in advance to improve the adhesion between the photosensitive resin composition or the photosensitive layer of the photosensitive material.
  • a coupling treatment a method described in Japanese Patent Application Laid-Open No. 2000-39033 is preferably used.
  • an oxygen-blocking protective layer can be further provided on the photosensitive layer for the purpose of improving the curing sensitivity by exposure.
  • the oxygen blocking film may have the same configuration as that described for the intermediate layer of the transfer photosensitive material. Thickness of oxygen barrier film 0.5 to 3.0 / 1 111 preferred.
  • the photosensitive layer is subjected to pattern exposure to perform an exposure step. By this exposure, the exposed area of the photosensitive layer is cured. Next, a pattern is formed on the photosensitive layer by the subsequent development process, and members such as color filter pixels or spacers can be formed as desired.
  • two-dimensional scanning is performed by modulating light based on image data using a spatial light modulation device in which light having a light source wavelength in the range of 350 nm to 420 nm is two-dimensionally arranged. This is performed by an exposure method for forming an image.
  • the exposure in the present invention is also referred to as a maskless exposure because it performs a scanning exposure represented by a laser direct imaging system (LDS) without using a mask pattern. More specifically, the maskless exposure applied to the present invention is based on image data. It can be said that exposure is performed to form a two-dimensional image by performing relative scanning while modulating light.
  • LDS laser direct imaging system
  • an ultrahigh pressure mercury lamp or a laser is used as a light source.
  • An ultra-high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube, etc., and has a higher vapor pressure of mercury to improve luminous efficiency (the mercury vapor pressure during lighting is very high). Some will be 5MPa; W. Elenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectra, i-line (365 nm), h-line (405 nm), and g-line (436 nm) are generally used for ultra-high pressure mercury lamps, and i-line with a wavelength of 365 nm is mainly used.
  • Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English.
  • a laser has an oscillator and an amplifier that produce monochromatic light with stronger coherence and directionality by amplifying and oscillating light waves, utilizing the phenomenon of stimulated emission that occurs in materials with an inversion distribution.
  • the excitation media include crystals, glass, liquids, dyes, and gases. From these media, the types of lasers are solid laser (YAG laser), liquid laser, gas laser (argon laser, He-Ne laser, carbon dioxide gas) Laser, excimer laser), and semiconductor laser. Such a known laser can be used for the exposure in the present invention.
  • a semiconductor laser emits light that induces and emits coherent light at a pn junction when electrons and holes flow into the junction due to carrier injection, excitation by an electron beam, ionization by collision, photoexcitation, etc.
  • a laser using a diode The wavelength of coherent light emitted thereby is determined by the semiconductor compound.
  • the wavelength of the laser is not particularly limited, but from the viewpoint of resolution, cost of the laser device, and availability, it is preferable to select from a wavelength range of 300 to 500 nm for semiconductor lasers. 450nm force S more preferred, 360-420nm more preferred.
  • YAG-SHG solid-state laser of 532 nm can be mentioned. More In the case of a semiconductor excitation solid-state laser, 532, 355, and 266 nm can be mentioned, and 355 nm is preferably selected from the viewpoint that the conventional photopolymerization initiator for resist has sensitivity.
  • KrF lasers at 249 nm and ArF lasers at 193 nm are used.
  • a light source with an exposure wavelength of 410 nm is used. The selection is preferable from the viewpoint of increasing the transmittance of the display region.
  • DMD digital 'Mike Mouth Mira. Device
  • This is a method using a spatial modulation element in which micromirrors are arranged in two dimensions, such as the optical semiconductor developed by Dr. et al.
  • the light from the light source is irradiated onto the DMD by an appropriate optical system, and the reflected light from each mirror arranged two-dimensionally on the DMD passes through another optical system on the photosensitive layer. It forms an image of two-dimensional light spots.
  • the light spot is not exposed between the light spots.
  • the image of the light spots arranged in two dimensions is moved in a slightly inclined direction with respect to the two-dimensional arrangement direction, the light spots in the first row are used.
  • the entire surface of the photosensitive layer can be exposed in such a manner that the light spot in the rear row is exposed between the light spot and the light spot.
  • the brightness of the light spot has only two gradations, ON and OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.
  • another typical method of the relative staggering method while modulating light in the present invention is a method using a polygon mirror.
  • a polygon mirror is a rotating member that has a reflection surface of a series of plane mirrors around it.
  • light from a light source is reflected and irradiated onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror.
  • By moving the substrate at a right angle to the strike direction the entire surface of the photosensitive layer on the substrate can be exposed.
  • the intensity of light from the light source in an appropriate way
  • An image pattern can be formed by controlling ON-OFF or halftone. By using a plurality of light from the light source, the scanning time can be shortened.
  • the exposure method in the present invention there are a method using an ultrahigh pressure mercury lamp and a method using a laser. The latter is preferable.
  • a known laser such as an argon laser, a He—Ne laser, a semiconductor laser, a carbon dioxide gas laser, or a YAG laser can be used.
  • the wavelength of the laser is not particularly limited, but in particular, it is preferable to select from a wavelength range of 300 to 500 nm from the viewpoint of the resolution of the dark color separation barrier, the cost of the laser device, and the availability. S, more preferably 340-450 nm, 360-420 nm force S, more preferred.
  • the laser beam diameter is not particularly limited, but from the viewpoint of the resolution of the dark color separation partition, 5-30 xm is preferred as the 1 / e 2 value of the Gaussian beam. I like it.
  • the amount of energy of the laser beam is not particularly limited, but from the viewpoint of exposure time and resolution, 1 to: 100 mj / cm 2 is preferable, and 5 to 20 mj / cm 2 is more preferable.
  • the scanning speed of the laser is not particularly limited as long as it satisfies the condition that the display characteristics of the color filter can be improved and the productivity is also high, but it is 5 mm / sec to 3000 m / sec. Force S is preferable, more preferably 10 mm / second to 2000 m / second, and most preferably 15 mmZ second to lOOOOmZ second. 5 mm / second or less is preferable because the number of exposure heads must be significantly increased in the highly productive exposure system aimed at by the present invention. Also, at 3000m / sec or more, the illuminance must be significantly increased, so it is not practical.
  • an exposure head provided with a light irradiation means and a light modulation means for the photosensitive layer, wherein the column direction of the picture element portions is relative to the strike direction of the exposure head.
  • An exposure head arranged to form a predetermined set inclination angle ⁇ is used.
  • exposure is performed by moving the exposure head relative to the photosensitive layer in the scanning direction.
  • the exposure head by specifying the pixel part to be used for N double exposure (where N is a natural number of 2 or more), among the usable pixel parts, by the use pixel part specifying means, With respect to the exposure head, the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure.
  • N double exposure refers to a straight line parallel to the scanning direction of the exposure head on the exposed surface in almost all of the exposed region on the exposed surface of the photosensitive layer.
  • the “light spot array (pixel array)” means a smaller angle with respect to the strike direction of the exposure head among light spots (pixels) arranged as a pixel unit generated by the pixel unit.
  • the arrangement of the picture element portions does not necessarily have to be a rectangular lattice, but may be an arrangement of a parallelogram, for example.
  • the "substantially all areas" of the exposure area is described because the pixel part row is inclined at the both side edges of each picture element part, so that the strike direction of the exposure head is Intersects with a straight line parallel to Since the number of picture element rows in the used picture element part is reduced, when a plurality of exposure heads are connected together in the case of force, a straight line parallel to the scanning direction may be formed due to errors in the mounting angle and arrangement of the exposure heads.
  • N double drawing is used as a term corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. And the term “multiple drawing” shall be used.
  • N is not limited as long as N is a natural number of 2 or more.
  • a force that can be appropriately selected according to the purpose A natural number of 3 or more is preferred. A natural number of 3 or more and 7 or less.
  • a force beam is preferred.
  • exposure can be performed using the following apparatus.
  • FIG. 1 shows the appearance of the exposure unit according to the present invention.
  • the exposure unit includes a flat stage 152 that holds a photosensitive material 150 by adsorbing a glass substrate to the surface.
  • Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154.
  • the stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 158 so as to be reciprocally movable.
  • the exposure apparatus is provided with a drive device (not shown) for driving the stage 152 along the guide 158.
  • a U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each end of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156.
  • a scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sections for detecting the front and rear ends of the photosensitive material 150 are provided on the other side.
  • Sensor 164 is provided.
  • the scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152.
  • the scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.
  • FIG. 2 shows the configuration of the scanner of the exposure unit according to the present invention.
  • FIG. 3A is a plan view showing an exposed region formed on the photosensitive material
  • FIG. 3B is a diagram showing an arrangement of exposure areas by each exposure head.
  • the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows r ⁇ lj (for example, 3 rows and 5 columns). .
  • m rows r ⁇ lj for example, 3 rows and 5 columns.
  • four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150.
  • An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the auxiliary running direction.
  • a strip-shaped exposed region 170 is formed for each exposure head 166 in the photosensitive material 150.
  • the exposure area by each exposure head arranged in the m-th row and the n-th column is indicated, it is expressed as an exposure area 168.
  • each of the exposure heads in each row arranged in a line so that the strip-shaped exposed areas 170 are arranged without gaps in the direction perpendicular to the sub-scanning direction They are arranged at a predetermined interval in the arrangement direction (natural number times the long side of the exposure area, twice here). Therefore, the exposure between the exposure area 168 and the exposure area 168 in the first row
  • Unexposed areas are exposed using the exposure area 168 in the second row and the exposure area 168 in the third row.
  • FIG. 4 is a perspective view showing a schematic configuration of the exposure head according to the present invention.
  • FIG. 5A is a cross-sectional view in the sub-scanning direction along the optical axis in the configuration of the exposure head shown in FIG. 4
  • FIG. 5B is a side view in the sub-scanning direction along the optical axis in the configuration of the exposure head shown in FIG. FIG.
  • each of the exposure heads 166 to 166 includes an incident light beam.
  • a digital micromirror device (DMD) 50 is provided as a spatial light modulation element that modulates the image for each pixel in accordance with image data.
  • the DMD 50 is connected to a controller (not shown) having a data processing unit and a mirror drive control unit.
  • the data processing unit of the error generator generates a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each exposure head 166 based on the input image data.
  • the area to be controlled will be described later.
  • the mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the image data processing unit. The control of the angle of the reflecting surface will be described later.
  • a fiber array light source having a laser emitting portion in which the emitting end portion (light emitting point) of the optical fiber is arranged in a line along the direction corresponding to the long side direction of the exposure area 168 66, a lens system 67 for correcting the laser light emitted from the fiber array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. Yes.
  • the lens system 67 is a pair of combination lenses 71 that collimates the laser light emitted from the fiber array light source 66, and corrects so that the light quantity distribution of the collimated laser light is uniform 1 It is composed of a paired combination lens 73 and a condensing lens 75 that condenses the laser light whose light intensity distribution is corrected on the DMD. In the arrangement direction of the laser emitting end of the combination lens 73, the portion close to the optical axis of the lens expands the light beam, and the portion away from the optical axis contracts the light beam and extends in a direction perpendicular to the arrangement direction. On the other hand, it has the function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.
  • lens systems 54 and 58 for forming an image of the laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150 are arranged.
  • the lens systems 54 and 58 are arranged so that the DMD 50 and the exposed surface 56 are in a conjugate relationship.
  • FIG. 6 is a partially enlarged view showing the structure of the DMD.
  • a micromirror (micromirror) 62 is disposed on an SRAM cell (memory cell) 60 supported by a support column.
  • the DMD 50 is a mirror device configured by arranging 1J of a large number (for example, 1024 ⁇ 768) micromirrors constituting a pixel (pixel) in a grid pattern. Each pixel is provided with a micromirror 62 supported by a support column at the top.
  • a highly reflective material such as aluminum is deposited on the surface of the micromirror 62.
  • the reflectance of the microphone mirror 62 is 90% or more.
  • a silicon gate CMOS SRAM cell 60 manufactured on an ordinary semiconductor memory manufacturing line is disposed through a support including a die and a yoke, and the entire structure is monolithic (integrated).
  • FIG. 7A shows a state in which the micromirror 62 is in an on state + tilt
  • FIG. 7B shows a state in which the micromirror 62 is tilted in an off state. Therefore, by controlling the tilt of the micromirror 62 in each pixel of the DMD 50 according to the image signal as shown in FIG. 6, the light incident on the DMD 50 is reflected in the tilt direction of each micromirror 62. .
  • Fig. 6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + or once. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. Note that a light absorber (not shown) is arranged in a direction in which the light beam is reflected by the micromirror 62 in the off state.
  • the DMD 50 is arranged with a slight inclination so that the short side thereof forms a predetermined angle ⁇ (for example, 1 ° to 5 °) with the sub-scanning direction.
  • ⁇ for example, 1 ° to 5 °
  • FIG. 8A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted
  • FIG. 8B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted.
  • DMD50 a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction.
  • a large number of groups (for example, 768) are arranged in the short direction.
  • the total running width W is almost the same.
  • the same scanning line is overlapped and exposed (multiple exposure) by different micromirror rows.
  • the multiple exposure allows fine control of the exposure position.
  • high-definition exposure can be realized.
  • joints between multiple exposure heads arranged in the main scanning direction can be connected without steps by minute control of the exposure position.
  • FIG. 9A is a perspective view showing the configuration of the fiber array light source
  • FIG. 9B is a partially enlarged view of FIG. 9A
  • FIGS. 9C and 9D are plan views showing the arrangement of light emitting points in the laser emitting section. .
  • the fiber array light source 66 includes a plurality (for example, six) of laser modules 64.
  • One end of a multimode optical fiber 30 is coupled to each laser module 64.
  • the other end of the multi-mode optical fiber 30 is coupled to a optical fiber 31 having the same core diameter as that of the multi-mode optical fiber 30 and a cladding diameter smaller than that of the multi-mode optical fiber 30.
  • the emission end portion (light emission point) of the optical fiber 31 is arranged in a line along the main scanning direction orthogonal to the sub-scanning direction to constitute a laser emission portion 68.
  • the light emitting points can be arranged in two rows along the main scanning direction.
  • the exit end of the optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface, as shown in FIG. 9B. Further, a transparent protective plate 63 such as glass is disposed on the light emitting side of the optical fiber 31 in order to protect the end face of the optical fiber 31.
  • the protective plate 63 may be disposed in close contact with the end face of the optical fiber 31 or may be disposed so that the end face of the optical fiber 31 is sealed.
  • the exit end portion of the optical fiber 31 has a high light density and is likely to collect dust and easily deteriorate. However, the protective plate 63 can prevent the dust from adhering to the end face and delay the deterioration.
  • a multimode optical fiber is provided between two multimode optical fibers 30 adjacent to each other with a large cladding diameter. 30 are stacked, and the output end of the optical fiber 31 coupled to the stacked multimode optical fiber 30 is connected to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large. So that it is sandwiched between the two exit ends. It is arranged.
  • FIG. 10 shows the configuration of the multimode optical fiber.
  • such an optical fiber has an optical fiber 31 with a small cladding diameter of length:! To 30 cm at the tip of the laser beam emitting side of the multimode optical fiber 30 with a large cladding diameter.
  • Force S can be obtained by coupling coaxially.
  • the two optical fibers are fused and joined to the incident end face force of the optical fiber 31 and the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide.
  • the diameter of the core 31a of the optical fiber 31 is the same as the diameter of the core 30a of the multimode optical fiber 30.
  • a short optical fiber obtained by fusing an optical fiber having a short length and a large cladding diameter to an optical fiber having a small cladding diameter is connected to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. May be combined.
  • the tip portion can be easily replaced when the optical fiber with a small diameter is broken, and the cost required for the exposure head maintenance can be reduced.
  • the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.
  • the multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber.
  • a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used.
  • the transmittance of the incident end face coating is 99.5% or more
  • the cladding thickness ⁇ (cladding diameter-one core diameter) Z2 ⁇ is set to the SOOnm wavelength band. Even if it is about 1/2 of the case where the infrared light is propagated and about 1Z4 when the infrared light in the wavelength band of 1.5 zm for communication is propagated, the propagation loss does not increase substantially. .
  • the cladding diameter of the optical fiber 31 is not limited to 60 / im.
  • the optical fiber used in conventional fiber light sources has a cladding diameter of 125 ⁇ .
  • the smaller the cladding diameter, the deeper the depth of focus. Therefore, the cladding diameter of the multimode optical fiber is preferably 80 / im or less, more preferably 60 zm or less, and even more preferably 40 zm or less.
  • the cladding diameter of the optical fiber 31 is preferably 10 ⁇ m or more.
  • the laser module 64 includes a combined laser light source (fiber light source) shown in FIG.
  • This combined laser light source is composed of a plurality of (for example, 7) chip-shaped lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged and fixed on the heat block 10.
  • And LD7, and GaN-based semiconductor laser 1 Collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of LD1 to LD7, and one condenser lens 20 And a multimode optical fiber 30.
  • the number of semiconductor lasers is not limited.
  • the GaN semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for the multimode laser and 30 mW for the single mode laser).
  • As the GaN-based semiconductor lasers LD1 to LD7 lasers having an oscillation wavelength other than the above 405 nm in the wavelength range of 350 nm to 450 nm may be used.
  • the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements.
  • the package 40 includes a package lid 41 that closes its opening. After the degassing process, a sealing gas is introduced, and the opening of the package 40 is closed by the package lid 41.
  • the combined laser light source is hermetically sealed in a closed space (sealed space) formed by the lid 41.
  • a base plate 42 is fixed to the bottom surface of the package 40. On the upper surface of the base plate 42, the heat block 10, the condensing lens holder 45 for holding the condensing lens 20, and the multimode light.
  • a fiber holder 46 that holds the incident end of the fiber 30 is attached. The exit end of the multimode optical fiber 30 is drawn out of the package through an opening formed in the wall surface of the package 40.
  • a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held.
  • An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.
  • FIG. 14 is a view showing a front shape of a mounting portion of the collimator lenses 11 to 17.
  • Each of the collimator lenses 11 to 17 is formed into a shape obtained by cutting an area including the optical axis of a circular lens having an aspherical surface into a long and narrow plane.
  • the elongated collimator lens can be formed, for example, by molding resin or optical glass.
  • the collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is perpendicular to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 14). .
  • the GaN-based semiconductor lasers LD1 to LD7 have an active layer with an emission width of 2 ⁇ m, and divergence angles in a direction parallel to and perpendicular to the active layer are, for example, 10 ° and 30 °, respectively. Lasers that emit laser beams B1 to B7 in the state are used. These GaN-based semiconductor lasers LD :! to LD7 are arranged so as to be arranged in a row of luminous point forces S1 in a direction parallel to the active layer.
  • each collimator lens 11-17 has a width of 1. lmm and a length of 4.6.
  • the horizontal and vertical beam diameters of the laser beams B1 to B7 incident on them are 0 ⁇ 9mm and 2.6mm, respectively.
  • the condensing lens 20 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a thin parallel plane, and perpendicular to the arrangement direction of the collimator lenses 11 to 17, that is, horizontally extending. It is formed in a short shape in any direction.
  • the condensing lens 20 is also formed, for example, by molding resin or optical glass.
  • each exposure head 166 of the scanner 162 the GaN-based semiconductor lasers LD:!
  • To LD7 that constitute the combined laser light source of the fiber array light source 66 are laser beams Bl, B2, B3,
  • Each of B4, B5, B6, and B7 is collimated by a corresponding collimator lens 11-: 17.
  • the collimated laser beams B1 to B7 are condensed by the condensing lens 20 and converge on the incident end face of the core 30a of the multimode optical fiber 30.
  • a condensing optical system is constituted by the collimator lenses 11 to 17 and the condensing lens 20, and a multiplexing optical system is constituted by the condensing optical system and the multimode optical fiber 30. That is, the laser beam B1 to B7 force condensed as described above by the condensing lens 20 is incident on the core 30a of the multimode optical fiber 30 and propagates through the optical fiber, and is combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.
  • the laser emitting part 68 of the fiber array light source 66 has a high-luminance light emitting point as shown above. It is arranged in a row along the heel direction. Laser light from a single semiconductor laser
  • the conventional fiber light source coupled to one optical fiber has a low output, a desired output could not be obtained unless a multi-row arrangement IJ is performed.
  • the combined laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.
  • a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser.
  • This fiber light source uses a multimode optical fiber with a core diameter of 50 xm, a clad diameter of 125 zm, and NA (numerical aperture) of 0.2 as an optical fiber.
  • 48 multimode optical fibers (8 x 6) must be bundled, and the area of the light emitting area is 0.62 mm 2 (0.675 mm x 0.925 mm). 1. 6 X 10 6 (W / m 2 ), brightness per optical fiber is 3.2 X 10 6 (W / m 2 ).
  • the fiber array light source according to the present invention, as described above, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be reduced.
  • the brightness at the laser emission ⁇ 68 is 123 X 10 6 (W / m 2 ), which is about 80 times higher than before. Is possible.
  • the luminance per optical fiber is 90 ⁇ 10 6 (W / m 2 ), which is about 28 times higher than the conventional one.
  • the bundled fiber light source of the exposure head has a diameter in the sub-scanning direction of the light emitting region of 0.675 mm.
  • the fiber array light source of the exposure head has a diameter in the sub scanning direction of the light emitting region. Is 0.025 mm.
  • the diameter of the light emitting region of the fiber array light source 66 is small in the sub-scanning direction, the light that passes through the lens system 67 and enters the DMD 50 The bundle angle is reduced. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deeper.
  • the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. The effect of this depth of focus becomes more prominent and effective as the required light quantity of the exposure head increases.
  • the size of one pixel projected on the exposure surface is 10 ⁇ ⁇ m.
  • DMD is a reflective spatial modulation element, but in FIG. 15A and FIG. 15B, development views are used to explain the optical relationship.
  • the image data force corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and stored in a frame memory in the controller.
  • This image data is data representing the density of each pixel constituting the image by binary values (whether or not dots are recorded).
  • the stage 152 having adsorbed the photosensitive material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown).
  • a driving device not shown
  • the stage 152 passes under the gate 160, the leading edge of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160.
  • the image data stored in the frame memory is sequentially read out for each of a plurality of lines, and a control signal is generated for each exposure head 166 based on the image data read out by the data processing unit.
  • the mirror drive control unit performs on / off control of each micromirror of the DMD 50 for each exposure head 166 based on the generated control signal.
  • the DMD 50 When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light is reflected when the micro mirror of the DMD 50 is in the on state. The reflected laser light is imaged on the exposed surface 56 of the photosensitive material 150 by the lens systems 54 and 58. In this manner, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the photosensitive material 150 is exposed in a pixel unit (exposure area 168) that is approximately the same number as the number of pixels used in the DMD 50.
  • the photosensitive material 150 when the photosensitive material 150 is moved at a constant speed together with the stage 152, the photosensitive material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is provided for each exposure head 166. Is formed.
  • FIGS. 16A and 16B Examples of the use area of the DMD 50 are shown in FIGS. 16A and 16B.
  • DMD50 has a micromirror in which 1024 micromirrors are arranged in the direction of the main runner.
  • the controller controls so that only a part of the microphone aperture mirror rows (for example, 1024 ⁇ 128 rows) is driven.
  • FIG. 16A it is possible to use a micromirror array arranged at the center of the DMD50.
  • FIG. 16B using a micromirror array arranged at the end of the DMD50. Moyore.
  • the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.
  • the data processing speed of DMD50 is limited, and the modulation speed per line is determined in proportion to the number of pixels used. The modulation speed per hit is increased. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.
  • modulation can be performed twice as fast per line as compared to using all 768 sets.
  • modulation can be performed three times faster per line than when all 768 pairs are used.
  • a 500mm area can be exposed in 17 seconds in the sub-scanning direction.
  • modulation can be performed 6 times faster per line. In other words, a 500mm area can be exposed in 9 seconds in the sub-scanning direction.
  • the number of micromirror rows to be used is preferably 10 to 200 force S, more preferably 10 to 100 force S. Since the area per micromirror corresponding to one pixel is 15 / im X 15 ⁇ m, when converted to the DMD50 use area, an area of 12 mm ⁇ 150 ⁇ m to 12 mm X 3 mm is preferable, 12 mm ⁇ 150 A region of ⁇ m to 12 mm ⁇ l.5 mm is more preferable.
  • the laser light emitted from the fiber array light source 66 can be made into substantially parallel light by the lens system 67 and irradiated to the DMD 50.
  • Figure 17A shows the DMD proper use area. As shown in FIG. 17A, it is preferable that the irradiation area of the laser beam by DMD50 coincides with the use area of DMD50. If the irradiation area is wider than the use area, the utilization efficiency of the laser beam is reduced.
  • the diameter of the light beam condensed on the DMD 50 in the sub-scanning direction needs to be reduced according to the number of micromirrors arranged in the sub-scanning direction by the lens system 67.
  • the number of micromirror arrays used is less than 10, the angle of the light beam incident on the DMD 50 is increased, and the depth of focus of the light beam on the stray surface 56 is not preferable.
  • the number of micromirror rows to be used is 200 or less, it is preferable from the viewpoint of modulation speed.
  • DMD is a reflection type spatial modulation element.
  • Figures 17A and 17B are developed views to explain the optical relationship.
  • the exposure unit includes a DMD in which 768 pairs of micromirror row force sub-scanning directions in which 1024 micromirrors are arranged in the main running direction.
  • the controller controls the micromirror array so that only a part of the micromirror array is driven. Therefore, since the modulation speed per line is faster than when driving all the micromirror rows, high-speed exposure is possible.
  • the exposure energy is appropriately selected depending on the composition of the photosensitive resin composition.
  • the crosslinking density in the photosensitive layer after curing is set to 0.003 mol Zg or more, and the crosslinking reaction rate is set to 86 to 100%. It is preferable to carry out the exposure under such energy conditions, even if a high, high cross-linking ratio is obtained.
  • the resulting pattern is subject to deformation due to external pressure.
  • good deformation recovery can be secured even when plastic deformation is caused by external pressure.
  • the spacer pixel is formed according to the present invention, the uniformity of the cell thickness is ensured even when the cell thickness is 2 to 4 ⁇ , and the liquid crystal display element displays Display unevenness in an image can be effectively prevented.
  • the formed pattern is excellent in uniformity and surface smoothness, there is an advantage that the resistance value is lowered and the operability is increased.
  • crosslinking density [mol / g] and the crosslinking reaction rate [%] in the present invention can be obtained by the following formula.
  • Crosslink density number of moles of crosslinkable group / mass of resin component
  • Cross-linking reaction rate [(initial cross-linking group amount minus one post-reaction cross-linking group amount) Z initial cross-linking group amount] X 100
  • the base amount is obtained by the IR method (“cross-linking group amount—IR absorption amount calibration curve with a known sample, and the cross-linking group amount is obtained from the IR absorption amount”) and calculated from the above formula.
  • the end of the cross-linking reaction can be ended with the end of the cross-linking reaction in the heat treatment step in the present invention.
  • the "resin portion” is a portion excluding these when solid fine particles such as pigment and silica are included.
  • the crosslink density is adjusted by adjusting the total amount (mole) of crosslinkable groups in the resin portion present in the photosensitive resin composition in the resin component constituting the photosensitive resin composition, that is, the kinder (A).
  • the total amount of crosslinkable groups or polymerizable groups in the ethylenically unsaturated compound (B) is not less than 0.0073 mol / g of the total amount (g) of the composition. By doing so, you can do what you can do.
  • Development can be carried out by a known alkali development method.
  • a solvent or an aqueous developer particularly an alkaline aqueous solution (alkaline developer)
  • the exposed photosensitive transfer material is immersed in a developing bath containing the developer, or photosensitive transfer. It can be carried out by spraying the layer on the material with a spray or the like, and further by rubbing with a rotating brush, a wet sponge, etc., or by treating with ultrasonic waves.
  • the liquid temperature of the developer is preferably 20 ° C to 40 ° C, and the pH of the developer is preferably 8 to 13: Also After the development, a washing treatment is preferably performed.
  • a development method a known method such as paddle development, shower development, shower & spin development, dip image, or the like can be used.
  • the uncured portion can be removed by spraying a developer onto the exposed photosensitive layer by shower.
  • a developer onto the exposed photosensitive layer by shower.
  • the alkaline aqueous solution used for dissolving the photosensitive layer, the thermoplastic resin layer, and the intermediate layer for example, a dilute aqueous solution of an alkaline substance is preferable. What added a small amount of water-miscible organic solvents is also preferable.
  • the alkaline substance is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples of the alkaline substance include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkalis such as sodium bicarbonate and potassium bicarbonate.
  • the concentration of the alkaline substance is preferably 0.01 to 30% by mass.
  • the pH is preferably 8 to 14:
  • a roller conveyor or the like is installed in the developing tank, and the substrate moves horizontally.
  • the photosensitive resin is preferably formed on the upper surface of the substrate.
  • the inclination angle is preferably 5 ° force 30 ° force S.
  • Post-exposure after development, prior to heat treatment is preferable from the viewpoints of controlling the cross-sectional shape of the image, controlling the hardness of the image, controlling the surface roughness of the image, and controlling the film thickness reduction of the image.
  • the light source used for the post-exposure include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp described in paragraph No. 0074 of Japanese Unexamined Patent Publication No. 2005-3861.
  • the substrate is directly irradiated with light from a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask or the like.
  • a light source such as an ultra-high pressure mercury lamp or a metal halide
  • Such post-exposure may be performed only on one side, but is performed on both sides as necessary.
  • the exposure amount can be appropriately adjusted in accordance with the above control purpose within the range of the upper surface: 100 to 2000 mj / square centimeter and the lower surface: 100 force to 2000 mJ / square centimeter.
  • a heat treatment is performed to react the monomer and the crosslinking agent contained in the photosensitive resin layer of the present invention, thereby ensuring the hardness of the image.
  • the heat treatment temperature is preferably in the range of 150 ° C to 250 ° C.
  • the heat treatment time is preferably 10 to 150 minutes. In this temperature range and heat treatment time, deterioration of color purity due to heat coloring of the resin can be suppressed while ensuring sufficient hardness of the image. Further, the heating conditions in the heat treatment may be changed depending on the color. Also, after all colors have been formed, a final heat treatment can be performed to stabilize the hardness. In that case, it is preferable in terms of hardness to carry out at a higher temperature (for example, about 240 ° C).
  • the water-miscible organic solvent can be appropriately selected depending on the purpose.
  • examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol-monoethylenoleatenole, and ethylene glycol-monoethanol.
  • n- butynoleatenole benzyl alcohol, acetone, methylethylketone, cyclohexanone, ⁇ -force prolacton, ⁇ -butarate ratataton, dimethylformamide, dimethylacetamide, hexamethylphosphoroleamide, lactate ethyl, Examples include methyl lactate, ⁇ -force prolatatam, and methylpyrrolidone.
  • the addition amount of the organic solvent having water miscibility is preferably 0.:! To 30% by mass.
  • the addition amount of the surfactant is preferably 0.01 to 10% by mass.
  • the photosensitive layer patterned by the above process is heat-treated so that the crosslinking reaction rate is 86 to 100% for the purpose of promoting polymerization or curing reaction in the cured region and improving pattern strength. can do.
  • the crosslinking reaction rate is 86 to 100% for the purpose of promoting polymerization or curing reaction in the cured region and improving pattern strength. can do.
  • crosslinking of the crosslinkable group of the resin portion in the layer polymeric monomer such as polymer substance monomer, oligomer, etc.
  • the crosslinking reaction rate can be adjusted to be in the range of 86 to 100%.
  • the crosslinking reaction rate is more preferably 90 to 100%, and most preferably 95 to 100%.
  • the heating temperature and the heating time can be set at a high temperature and in a short time so that yellowing due to heat treatment is small and production tact is not reduced.
  • a photosensitive material having a photosensitive layer of a photosensitive resin composition having a crosslink density of 0.0073 mol / g or more is prepared, and the protective film is prepared.
  • the surface of the photosensitive layer that has been removed and exposed is superimposed on the substrate surface, laminated and bonded, and the temporary support is peeled and removed at the interface with the thermoplastic resin layer.
  • the optical layer is transferred (layer formation process).
  • the photosensitive layer is exposed through a predetermined mask through the thermoplastic resin layer and the intermediate layer, and unexposed portions of the photosensitive layer are developed and removed with an alkaline aqueous solution to form a spacer pattern (patterning).
  • a photospacer can be obtained by applying heat treatment to the formed spacer pattern and curing the exposed portion (heat treatment step) so that the crosslinking reaction rate is 86 to 100%.
  • a photospacer produced by the method for producing a photospacer of the present invention is composed of a photosensitive resin composition having a crosslink density of 0.0073 mol / g or more or the photosensitive resin composition.
  • the photosensitive layer is cured to a crosslinking reaction rate of 86 to 100%.
  • the photo spacer exhibits a high level of deformation (preferably 70% or more) when plastically deformed, and has sufficient mechanical properties, so that the cell thickness of the liquid crystal cell is kept uniform. It is effective.
  • this photo spacer can be suitably used for a display device that easily causes display unevenness due to a variation in the cell thickness of the liquid crystal cell.
  • the spacer not only the spacer but also the pixel itself can be produced by the pattern forming method of the present invention. That is, on the transparent substrate such as a glass substrate, the pixels of the three primary colors of RGB can be arranged in a mosaic shape or a stripe shape by the pattern forming method according to the present invention.
  • each pixel is not particularly limited, and can be appropriately selected according to the purpose.
  • each pixel for example, a lattice pattern having a side of 40 to 200 ⁇ or a stripe pattern having a width of 40 to 200 / m can be easily formed. It is also possible to form higher definition patterns according to the exposure accuracy.
  • a black matrix is formed by exposure and development using a photosensitive layer colored in black on a transparent substrate.
  • a photosensitive layer colored in one of the three primary colors of RGB exposure and development are sequentially repeated for each color in a predetermined arrangement with respect to the black matrix, and RGB on the transparent substrate. It is also possible to form a color filter in which the three primary colors are arranged in a mosaic or stripe form.
  • the liquid crystal display element of the present invention comprises a color filter obtained by the method for producing a color filter of the present invention.
  • the liquid crystal display element includes at least one of a pair of substrates that are light transmissive (including the substrate for a liquid crystal display device of the present invention) and a liquid crystal driving means (simple matrix driving method and active matrix driving). Moving system).) At least.
  • the liquid crystal display element substrate has a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.
  • the color filter substrate is provided with a photospacer having a uniform height and excellent deformation recovery. For this reason, the liquid crystal display device provided with the color filter substrate can suppress the occurrence of cell gap unevenness (cell thickness variation) between the color filter substrate and the counter substrate, and can effectively prevent display unevenness such as color unevenness. Can be prevented. Thereby, the produced liquid crystal display element can display a vivid image.
  • a photospacer is formed on a display light shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT.
  • a transparent conductive layer transparent electrode
  • a liquid crystal alignment film such as polyimide may be provided between a light shielding portion for display such as a black matrix or a driving element such as TFT and a photospacer. Good.
  • the substrate for a liquid crystal display device has, for example, a display spacer in which a photospacer is provided on the substrate in advance when the photospacer is provided on a display light-shielding portion or a driving element. It can be manufactured so as to cover the light shielding portion (black matrix or the like) and the driving element.
  • the present invention can be achieved by laminating a photosensitive layer of a photosensitive transfer material on a substrate surface, peeling and transferring it to form a photosensitive layer, and then subjecting it to exposure, development, heat treatment, etc. to form a photospacer.
  • a substrate for a liquid crystal display device can be produced.
  • colored pixels of three colors such as red (R), blue (B), and green (G), black matrix, and the like can also be provided by the manufacturing method of the present invention.
  • At least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving means between a pair of light-transmitting substrates (including the substrate for a liquid crystal display device of the present invention).
  • the liquid crystal driving means has an active element (for example, TFT), and a pair of The space between the substrates is uniform to a predetermined width by a photospacer having a uniform height and excellent deformation recovery.
  • the substrate for a liquid crystal display device of the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.
  • liquid crystals examples include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
  • the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, three-color pixels, or four-color or more pixels.
  • three colors it consists of three hues: red (R), green (G), and blue (B).
  • R red
  • G green
  • B blue
  • the pixel groups of RGB 3 colors the arrangement of mosaic type, triangole type, etc. is preferable.
  • the black matrix may be formed as described above, or conversely, the pixel group may be formed after forming the black matrix. Les.
  • Japanese Patent Application Laid-Open No. 2004-347831 can be referred to.
  • the liquid crystal display element of the present invention is suitably used for an LED display device.
  • Liquid crystal display modes of liquid crystal display devices include STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Those are preferred.
  • a display mode in which display unevenness is likely to occur due to fluctuations in the cell thickness of the liquid crystal cell for example, a cell thickness of 2 to 4 ⁇ .
  • a display mode of a certain VA type display mode, IPS type display mode, or OCB type display mode it is preferable because suppression of display unevenness can be efficiently achieved.
  • the basic configuration of the liquid crystal display device includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer).
  • a counter substrate provided with a photo spacer, and a liquid crystal material sealed in the gap
  • a counter substrate provided with a drive substrate and a counter electrode (conductive layer)
  • the liquid crystal display device of the present invention is suitable for various liquid crystal display devices, such as a structure in which a plate is placed opposite to each other with a photospacer interposed, and a liquid crystal material is sealed in the gap. Can be applied to.
  • the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Side Industry Research Committee, 1994)".
  • the liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display element of the present invention.
  • the liquid crystal display device of the various types described in the “next-generation liquid crystal display technology” can be configured. .
  • it is effective for constructing a color TFT liquid crystal display device.
  • a color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.
  • the liquid crystal display device includes the electrode substrate, polarizing film, retardation film, knock light, spacer, viewing angle compensation film, antireflection film, light diffusion, except that the liquid crystal display device of the present invention is provided. It can be generally constructed using various members such as a film and an antiglare film. For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals' Kayaba (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Volume 2)” , Fuji Chimera Research Institute, Ltd., 2003, etc.) ”. In this book of Itoda, all the disclosures of the present application 2005-222261 and 2005-368716 are incorporated by reference.
  • the combination of the transfer method and the LED backlight will be described in detail.
  • it may be carried out by a coating method using a slit coater or the like, and the backlight may be constituted by using a cold cathode tube.
  • an MVA mode liquid crystal display device configured as shown in FIG. 19 was produced.
  • thermoplastic resin layer coating solution consisting of the following formulation HI is applied and dried to make a thermoplastic resin: A layer was formed.
  • an intermediate layer coating solution having the following formulation p1 was applied onto this thermoplastic resin layer and dried to laminate an intermediate layer (oxygen barrier film).
  • a colored photosensitive resin composition K1 having the composition described in the following Table 1 (transfer method) was applied and dried to laminate a photosensitive layer.
  • the dry film thickness of the photosensitive layer of 15 dry film thickness and the thermoplastic resin layer m is 1.
  • 6 mu intermediate layer dry film thickness of m is 2. 4 M m
  • a protective film (12 xm polypropylene film) was pressure-bonded on the photosensitive layer.
  • Methyl ethyl ketone 53 37 26 35 37 26 41 Cyclohexanone--1.3--1.3-Binder 1 9.1 1 3.0--2.5-Binder 2 1 0.8--0.7--Binder 3---16.9--19
  • Sensitizing dye (A- 2) (NBCA) Note 2) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15
  • photosensitive resin transfer material K1 As described above, a photosensitive resin transfer material having a laminate structure formed by laminating a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a black (K) photosensitive layer was produced. (Hereinafter referred to as photosensitive resin transfer material K1).
  • thermoplastic resin layer HI [Prescription for coating solution for thermoplastic resin layer HI]
  • the composition of the colored photosensitive resin composition K1 used for the production of the obtained photosensitive resin transfer material K1 was changed to the colored photosensitive resin composition Rl having the composition described in Table 1 (transfer method).
  • Photosensitive resin transfer materials Rl, G1 and B1 were produced in the same manner as described above except that G1 and B1 were replaced.
  • the exposed photosensitive layer is overlaid so as to contact the surface of the glass substrate heated at 100 ° C for 2 minutes, and the laminator Lamicll type [ (Manufactured by Hitachi Industries, Ltd.) was laminated under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min.
  • the PET temporary support was peeled off and transferred onto a glass substrate.
  • the photosensitive layer is irradiated and exposed to obtain a pattern in which a hole is formed. Some areas of were cured.
  • DMD50 controlled so as to drive only the number of rows in the 1024 X use region, and a microlens whose one surface is a toric surface 66
  • a pattern forming apparatus having a microlens array 69 arranged in an array and an optical system 67 for forming an image of light passing through the microlens array 69 on the photosensitive layer was used.
  • the aperture array arranged in the vicinity of the condensing position of the microlens array is arranged so that only light having passed through the corresponding microlens is incident on each aperture.
  • triethanol amine developing solution [triethanolamine ⁇ Min 30 mass 0/0, polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate over preparative, 0.1 weight stearyl ether in total
  • the stock solution was prepared by mixing with the composition of the remaining pure water and stored. This stock solution was diluted 12 times with pure water (mixed at a ratio of 1 part by weight of the stock solution and 11 parts by weight of pure water) at 30 ° C for 50 seconds with a flat nozzle pressure of 0.04 MPa.
  • shower development was performed to remove the thermoplastic resin layer and the intermediate layer.
  • the glass substrate 911 on which the K image 916 was formed was again cleaned with a brush as described above, and then washed with pure water. After that, the silane coupling solution was not used and the substrate was preheated to 100. Heated at ° C for 2 minutes.
  • the glass substrate 911 on which the K image 916 is formed is coated with the photosensitive resin transfer material R1 obtained above, and the same process as the formation of the K image 916 is performed, so that the K image 916 of the glass substrate 911 is obtained.
  • a red pixel (R pixel) was formed on the side where the is formed.
  • the amount of exposure in the exposure process was 30 mj / cm 2, and shower development with a sodium carbonate developer was performed at 35 ° C for 35 seconds.
  • the thickness of the R pixel is 2.0 ⁇ im, and C. I. pigment 'red (C. I. P. R.) 254,
  • Each coating amount of CIPR 177 0 ⁇ 88g / m 2 was 0. 22g / m 2.
  • the glass substrate 911 on which the R pixel is formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and without using a silane coupling liquid. Heated at 100 ° C for 2 minutes with a heating device.
  • the same process as the formation of the K image 916 is performed.
  • the R pixel, and the like are formed.
  • Green pixels (G pixels) were formed.
  • the exposure amount in the exposure process is 30mjZcm 2
  • the thickness of the G pixel is 2. O x m, and C. I. Pigment 'Green (C. I. P. G.) 36
  • CIPY 150 is applied 1.12gZm 2 , 0 respectively .
  • the glass substrate 911 on which the R pixel and the G pixel were formed was again cleaned with a brush using a cleaning agent as described above, followed by shower cleaning with pure water, and without using a silane coupling liquid. Then, the substrate was heated at 100 ° C. for 2 minutes by a substrate preheating device.
  • the same process as the formation of the K image 16 is performed, and the K image 916 and the R pixel and the G pixel of the glass substrate 911 are formed.
  • a blue pixel (B pixel) was formed on the side.
  • the exposure dose in the exposure process was 30 mjZc m 2
  • shower development with a sodium carbonate-based developer was performed at 36 ° C. for 40 seconds.
  • the thickness of the B pixel is 2. O z m, and C. I. Pigment 'Blue (C. I. P. B.) 15:
  • the amount of CI pigment 'Violet (CIPV) 23 applied is 0.63 g / m 2 each.
  • the glass substrate 911 on which the R, G, and B pixels were formed was baked at 240 ° C for 50 minutes to obtain a color filter 912.
  • an ITO (Indium Tin Oxide) film 913 was formed thereon as a transparent electrode by sputtering, and a color filter substrate 910 was obtained.
  • K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 were weighed out, mixed at a temperature of 24 ° C. ( ⁇ 2 ° C.), and stirred at 150 r.p.m. for 10 minutes.
  • methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2- ( ⁇ _black mouth phenyl) _4,5-diphenylimidazole dimer, sensitization in the amounts shown in Table 1 above Dye (A_2) (NBCA), N_phenyl_2_mercaptobenzimidazole, and Surfactant 1 are weighed out and added in this order at a temperature of 25 ° C ( ⁇ 2 ° C) to a temperature of 40.
  • a colored photosensitive resin composition K1 was obtained by stirring at C ( ⁇ 2. C) and 150 r.p.m. for 30 minutes.
  • R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 (Transfer method) are removed and mixed at a temperature of 24 ° C ( ⁇ 2 ° C). Stir at 150 rpm for 10 minutes. Next, the amount of methyl ethyl ketone, binder 2, DPHA solution, 2- (o_clophenyl) _4,5-diphenylimidazole dimer, sensitizing dye (A_ 2) ( NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine, temperature 24. C ( ⁇ 2. C) was added in this order, and the mixture was stirred at 150 rpm for 10 minutes.
  • the amount of additive 1 shown in Table 1 is weighed, mixed at a temperature of 24 ° C. ( ⁇ 2 ° C.), stirred at 150 rpm for 20 minutes, and further the amount of interface shown in Table 1 above Activator 1 is weighed out and added at a temperature of 24 ° C ( ⁇ 2 ° C) and stirred at 30 rpm for 30 minutes
  • the colored photosensitive resin composition Rl was obtained by filtering with nylon mesh # 200. Details of each composition in the composition R1 shown in Table 1 are as follows. The compositions of the DPHA solution and the surfactant 1 are the same as those of the colored photosensitive resin composition K1.
  • composition G1 The details of each composition in the composition G1 described in Table 1 are as follows.
  • the composition of the binder 1, the DPHA liquid, and the surfactant 1 is the same as that of the colored photosensitive resin composition K1.
  • G pigment dispersion 1 “trade name: GT 2” manufactured by Fuji Film Electronics Materials Co., Ltd. was used.
  • composition B1 Details of each composition in the composition B1 described in Table 1 are as follows.
  • the composition of DPHA solution and surfactant 1 is the same as that of the colored photosensitive resin composition K1. * B pigment dispersion 1
  • PET temporary support polyethylene terephthalate film temporary support
  • the intermediate layer coating solution having the above-mentioned formulation P1 was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 ⁇ .
  • the cover film of the resulting photosensitive transfer sheet for spacer (1) is peeled off, and the exposed surface of the photosensitive layer is made of the above-mentioned IT film strength S sputter-formed color filter substrate 10 film 13 were laminated and laminated using a laminator type Lamic II (manufactured by Hitachi Industries, Ltd.) under a heating condition of a linear pressure of 100 NZcm and a temperature of 130 ° C. at a conveyance speed of 2 mZ. Thereafter, the PET temporary support was peeled off at the interface with the cushion layer, and the photosensitive layer was transferred together with the thermoplastic resin layer and the intermediate layer (photosensitive layer forming step).
  • a laminator type Lamic II manufactured by Hitachi Industries, Ltd.
  • the photosensitive layer on the substrate was exposed with a spacer pattern corresponding to 10 mj / cm 2 .
  • a pattern forming apparatus described below was performed at 405 nm.
  • the scanning speed at this time was 50 mm / sec.
  • DMD50 controlled so as to drive only the number of rows in the 1024 X use region
  • the micro lens array 69 and the micro lens array A pattern forming apparatus having an optical system 67 for forming an image of light passing through the sensor array 69 on the photosensitive layer was used.
  • the exposed photosensitive layer is allowed to stand at room temperature for 10 minutes, and then the entire surface of the photosensitive layer is coated with KOH developer (KOH, nonionic surfactant) manufactured by Fuji Film Electronics Materials Co., Ltd. , Trade name: CDK-1) was used for shower development at 25 ° C for 60 seconds to dissolve and remove uncured areas. Subsequently, ultrapure water was sprayed from the ultrahigh pressure washing nozzle at a pressure of 9.8 MPa to remove the residue, and then ultrapure water was sprayed from both sides with the shower nozzle to adhere to the developed film. The liquid and the dissolved photosensitive resin layer were removed and drained with an air knife to obtain a spacer pattern. The resulting spacer pattern was a transparent column having a diameter of 16 zm and an average height of 3.7 zm.
  • the color filter substrate 910 provided with the spacer pattern was subjected to a heat treatment at 230 ° C. for 30 minutes (heat treatment step) to produce a photospacer 914.
  • thermoplastic resin layer coating solution having the same formulation as Formula A is applied and dried, resulting in a dry film thickness of 15 ⁇ .
  • the thermoplastic resin layer was provided.
  • an intermediate layer coating solution having the same prescription power as that of the prescription cocoon was applied and dried to provide an intermediate layer having a dry film thickness of 1.6 ⁇ .
  • a projection forming coating solution having the following formulation C is prepared, and this projection forming coating solution is applied on the intermediate layer and dried to control the liquid crystal alignment with a dry film thickness of 2.0 / im.
  • a photosensitive layer for protrusions was coated.
  • a 12 ⁇ m-thick polypropylene film was attached to the surface of the photosensitive layer as a protective film.
  • a photosensitive transfer material for protrusions was produced in which a thermoplastic resin layer, an intermediate layer, a photosensitive layer for protrusions, and a protective film were laminated on the PET temporary support in order of the side force of the PET temporary support.
  • Photosensitive transfer material force for protrusions obtained from the above method Peel off the protective film, and overlay the exposed surface of the exposed photosensitive layer for protrusions with the surface of the color filter substrate 910 on which the ITO film 913 is provided (on the color filter).
  • Laminator Lamic type II manufactured by Hitachi Industries, Ltd.
  • Laminator Lamic type II was used and bonded together under the conditions of a linear pressure of 100 NZcm, a temperature of 130 ° C, and a conveying speed of 2.2 mZ (laminate). Thereafter, only the PET temporary support of the photosensitive transfer material for protrusions was peeled and removed at the interface with the thermoplastic resin layer. At this time, the photosensitive layer, the intermediate layer, and the thermoplastic resin layer are laminated on the color filter substrate in the order of the substrate side force.
  • thermoplastic resin layer which is the outermost layer
  • development was performed in the same manner as described above to dissolve and remove the thermoplastic resin layer and the intermediate layer.
  • the photosensitive layer for protrusions was not substantially developed.
  • an aqueous solution containing 0.085 mol / L sodium carbonate, 0.085 mol / L sodium bicarbonate and 1% sodium dibutylnaphthalenesulfonate was further sprayed at 33 ° C for 30 seconds using a shower type developing device. Then, development was performed, and unnecessary portions (uncured portions) of the protrusion photosensitive layer were developed and removed.
  • a projection 915 made of a photosensitive layer for projection patterned in a desired shape was formed on the color filter (RGB pixel).
  • the color filter substrate 910 on which the protrusions 915 are formed is beta-treated at 240 ° C for 50 minutes, so that the vertical cross-sectional shape is 1.5 ⁇ m high on the color filter (RGB pixel). Protrusions for controlling the liquid crystal orientation were formed.
  • a TFT substrate 921 was prepared as a counter substrate.
  • an ITO (Indium Tin Oxide) film 922 is formed by sputtering.
  • an alignment film 924 made of polyimide was provided on the IT film 922 of the TFT substrate and on the film 913 of the color filter substrate 910 on the side where the photospacer 914 was provided.
  • an epoxy resin sealant is printed at a position corresponding to the outer frame of the black matrix 916 provided around the pixel group of the color filter, and the color filter substrate 910 is connected to the TFT substrate 921. Pasted together.
  • the two bonded substrates were heat treated to cure the sealant, and a laminate of the two substrates was obtained.
  • This stack After degassing the body under vacuum, the pressure was returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates. After the completion of the injection, an adhesive was applied to the injection port portion, and the liquid injection cell was sealed by irradiating with ultraviolet rays to obtain a liquid crystal cell.
  • Polarizing plates (HLC2 — 2518, manufactured by Sanritsu Co., Ltd.) 9 25, 923 were shelled on both sides of the liquid crystal cell thus obtained.
  • a side-light type backlight was constructed using a chip-type LED) and placed on the back side of the liquid crystal cell provided with the polarizing plate to produce the MVA mode liquid crystal display device of the present invention. .
  • Example 2 In the same manner as in Example 1 except that the formulation of the coating solution for the photosensitive layer for forming RGBK and spacer in Example 1 was changed as follows, the photosensitive transfer sheet for spacers ( 2) and a comparative MVA mode liquid crystal display device were prepared: In the case of K and spacer-forming photosensitive layer coating solutions, a photopolymerization initiator and a spectral sensitizer were added to 2, 4 bis (tric). 6- [4— (N, N bisethoxycarbonylmethyl) 3-bromophenyl] s In the case of R and G photosensitive layer coating solutions, instead of triazine, a photopolymerization initiator and a spectral sensitizer are added with 2 trichloromethyl.
  • photopolymerization initiator and And the spectral sensitizer was replaced with 2 trichloromethyl-5- (p-styrylstyryl) 1, 3,4-oxadiazole.
  • the thickness of the cured region of the remaining photosensitive layer was measured.
  • a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. From the sensitivity curve thus obtained, the thickness of the cured region on the substrate was 1. The amount of light energy when the surface of the cured region was a glossy surface was determined as the amount of light energy required to cure the photosensitive layer.
  • the gray display when a gray test signal was input was observed visually and with a loupe, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
  • sheet resistance was measured by the four probe method using “Loresta” manufactured by Mitsubishi Oil Chemical Co., Ltd., and the value was defined as IT 0 resistance value. The lower the value, the better.
  • time required for exposure process The time until the exposure process of one color filter was completed was measured and described as “time required for exposure process” in the table below. It can be seen that the shorter this time, the higher the productivity.
  • Example 1 7 mJ / cm 2 A 8 Q / sq 3 minutes
  • Example 2 65 mj / cm 2 B 15 Q / sq 3 minutes
  • Example 3 A 9 Q / sq 3 minutes
  • Example 4 A ⁇ ⁇ ⁇ / sq 3 minutes Comparative Example 1 225 mj / cm 2 C 25 Q / sq 3 minutes Comparative Example 2 A 13 Q / sq 30 minutes
  • Example 2 As shown in Table 2, in Example 1, the used photosensitive resin composition was cured with high sensitivity, and even with LDI exposure by high-speed scanning, high-definition black matrix, RGB pixels, And the photospacer was completed. It was also found that the completed color filter provides high-quality display with no missing pixels and display unevenness. In addition, it was confirmed that high-speed response is possible because of low ITO resistance. Furthermore, it took about 3 minutes to complete the exposure process of one color filter, and it was found that the photosensitive resin composition was compatible with a highly productive system.
  • the color filter of Comparative Example 1 in which the black matrix, the RGB pixels, and the photosensitive layer for the photospacer using the photosensitive resin composition described in the prior art were subjected to LDI exposure by high-speed scanning was Since the curing sensitivity is low, a large amount of energy is required for curing, and the obtained color filter also has a high ITO resistance with pixel defects and display unevenness.
  • Example 2 Application (liquid registration) method
  • a 680 X 880 mm size non-alkali glass substrate (hereinafter simply referred to as a glass substrate) was cleaned with a 1 V cleaning device, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water.
  • This glass substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state. Thereafter, the glass substrate is cooled, adjusted to 23 ° C., and then coated with a glass substrate coater with a slit-shaped nose 1 MH-1600 (manufactured by F'S Japan Co., Ltd.). Resin composition K1 was applied.
  • vacuum dryer VCD manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • a part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film, and pre-betaged at 120 ° C. for 3 minutes to form a photosensitive layer K1 having a film thickness of 2.4 / im.
  • the light modulation means arranged in 768 pairs in the sub-scanning direction 1024 X DMD50 controlled to drive only the number of columns in the use area, and one surface passed through the toric mouth lens array 69.
  • a pattern forming apparatus having an optical system 67 that forms an image of light on the photosensitive layer was used.
  • KOH containing nonionic surfactant, product name: CDK-1 Fuji Film Elect Mouth Materials Co., Ltd.
  • a KOH-based developer (KOH, containing nonionic surfactant, product name: CDK-1) Fuji Film Elect Mouth Materials Co., Ltd.) was spray-developed from a flat nozzle at 23 ° C and a nozzle pressure of 0 ⁇ 04 MPa for 80 seconds to obtain a black pattern (developing process).
  • ultrapure water is sprayed onto the glass substrate on which the black pattern is formed with an ultrahigh pressure cleaning nozzle at a pressure of 9.8 MPa to remove the residue, and a black (K) image is formed on the alkali-free glass substrate. did.
  • heat treatment (beta) was performed at 220 ° C for 30 minutes.
  • the colored photosensitive resin composition R2 having the composition shown in the above (Liquid Registration Method) on the glass substrate on which the K image is formed, coating, exposing, developing, and beta in the same manner as the formation of the K image.
  • the exposure dose in the exposure process was 90 mj / cm 2
  • the shower image in the development process was 60 ° C. at 23 ° C.
  • the thickness of the R pixel is 1 ⁇ 6 / im, and the application amounts of CI pigment 'red (CIPR) 254 and CIPR 177 are respectively. 88 gZm 2 and 0.22 gZm 2 .
  • a colored photosensitive resin composition G2 having the composition shown in Table 1 (Liquid Registration Method) is used on the glass substrate on which the K image and the R pixel are formed, and similarly to the formation of the K image. Coating, exposure, development, and beta were performed, and green pixels (G pixels) were formed on the side of the glass substrate on which the K image and R pixels were formed.
  • the exposure amount in the exposure process was 90 mJ / cm 2
  • shower development in the development process was 60 ° C. at 23 ° C.
  • the thickness of the G pixel is 1.6 xm, and the application amounts of CI Pigment 'Green (CIPG) 36 and CI Pigment' Yellow (CIPY) 150 are 1.12gZm 2 and 0.48g / m 2 , respectively. Met.
  • the K image is formed.
  • coating, exposure, development, and beta were performed, and blue pixels (B pixels) were formed on the side of the glass substrate on which the K image, R pixels, and G pixels were formed.
  • the exposure amount in the exposure process was 90 mj / cm 2
  • the shower development in the development process was 60 ° C. at 23 ° C.
  • the thickness of the B pixel is 1 ⁇ 6 / im, and C. I. Pigment 'Blue (C. I. P. B.) 15:
  • the colored photosensitive resin compositions G2 and B2 were prepared in accordance with the colored photosensitive resin composition G1.
  • Colored photosensitive resin composition R2 was prepared as follows. R Pigment Dispersion 1, R Pigment Dispersion 2, Propylene Glycol Monomethyl Ether Case in the amounts listed in Table 1 (Liquid Residue Method) The tate was removed by force, mixed at a temperature of 24 ° C ( ⁇ 2 ° C), and stirred at 150 rpm for 10 minutes.
  • the amount of methyl ethyl ketone, binder 2, DPHA solution, 2 (o-clophenyl) -4,5-diphenylimidazolurnimer, sensitizing dye A-2) (NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine are weighed and added in this order at a temperature of 24 ° C ( ⁇ 2 ° C) and stirred at 150 rpm for 30 minutes. did. Further, the above-mentioned amount of Surfactant 1 is weighed out, added at a temperature of 24 ° C ( ⁇ 2 ° C), stirred at 30 rpm, filtered for 30 minutes, and filtered through nylon mesh # 200. The product R2 was obtained.
  • R pigment dispersion 1, R pigment dispersion 2, binder 1-2, DPHA liquid, and surfactant 1 in the colored photosensitive resin composition R2 are as described above.
  • An ITO film was formed as a transparent electrode on the color filter produced as described above by sputtering to obtain a color filter substrate.
  • the above-mentioned prescription is made with a glass substrate coater MH-1600 (manufactured by F'S Asia Co., Ltd.) having a slit nozzle.
  • a coating solution for photosensitive layer was applied.
  • V CD vacuum dryer
  • part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film, and then pre-betaged at 120 ° C for 3 minutes. 2.
  • a 4 ⁇ ⁇ ⁇ photosensitive layer was formed (layer formation process).
  • a photospacer was formed on one substrate of the color filter by the same patterning process and heat treatment process as in Example 1.
  • the exposure dose was 70 mj / cm 2 and development with the developer was 23 ° C for 60 seconds.
  • Example 2 After the photospacer was fabricated, the color filter substrate was used in the same manner as in Example 1 to fabricate the MVA mode liquid crystal display device of the present invention (see Fig. 19).
  • the MVA mode liquid crystal display device obtained in Example 2 was evaluated for curing sensitivity, display unevenness, and ITO resistance value in the same manner as in Example 1. The results are shown in Table 2 above. As is clear from Table 2, in Example 2, a photospacer was formed with high sensitivity as in Example 1, and the obtained liquid crystal display device showed no display unevenness and high image quality. Images are obtained and I The TO resistance value was also low.
  • Modified exposure method A polygon mirror type exposure apparatus that converts light emitted from a 405 nm LD into scan light by the rotation of a hexagonal polygon mirror was used. The scanning speed by the polygon mirror on the substrate was 300mZ seconds.
  • Example 3 As is apparent from Table 2, also in Example 3, a photospacer was formed with high sensitivity as in Examples 1 and 2, and the obtained liquid crystal display device had no display unevenness. Not recognized, a high-quality image was obtained, and the ITO resistance value was low.
  • a color filter was produced according to the same formulation and procedure as in Example 1 except that the exposure apparatus and exposure method were changed as follows.
  • Modified exposure method as the light irradiation means, a combined laser single light source shown in FIG. 9 and FIG. 10 to 14; and as the light modulation means, as shown in the schematic diagram of FIG. Micromirror column force with 1024 microphone mirrors 62 arranged in the direction 1024 of 768 pairs arranged in the sub-scanning direction DMD50 controlled to drive only the number of columns in the used area, and Fig. 5
  • An exposure apparatus provided with an exposure head 166 having an optical system for imaging the light shown in FIG.
  • each exposure head 166 that is, each DMD 50 is set to be smaller than the angle ⁇ at which double exposure is performed using 10 24 rows x 256 rows of micromirrors 62 that can be used.
  • This angle ⁇ is the number of N exposures, N
  • the constant inclination angle ⁇ for example, 0.50 degrees was adopted.
  • Example 2 The same procedure was used except that the scanning speed was changed to 2 mm / sec from the exposure method of Example 1 using RGBK and spacer forming photosensitive transfer material prepared by the same formulation and procedure as Example 1. A color filter was produced. In the liquid crystal display device obtained in this Comparative Example 2, display unevenness was not observed, a high-quality image was obtained, and the ITO resistance value was low. It took 0 minutes, and the productivity was high.
  • the photosensitive resin composition of the present invention is useful for forming partition walls, spacers, pixels, black matrices, and the like of liquid crystal cells. Using this photosensitive resin composition, it is possible to produce a color filter having excellent uniformity in pixel and cell thickness, a high-definition pattern, and less display unevenness. Furthermore, the color filter of the present invention is capable of high-speed response and is useful for producing a high-quality LCD display element.
  • Exposure head Exposure 0 according to the present invention .
  • Color filter substrate

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Abstract

Composition de résine photosensible utilisée dans un élément d'affichage à cristaux liquides, la composition comprenant (A) un liant, (B) un composé insaturé éthyléniquement, (C) un initiateur de photopolymérisation comprenant un composé hexaarylbiimidazole, (D) un sensibilisateur au spectre et (E) un donneur d’hydrogène, capable d’être vulcanisée par un système de photoexposition dans lequel la résine est soumise à un balayage relatif tandis que la lumière est modulée dans une plage de longueurs d'ondes de la source lumineuse comprise entre 350 nm et 420 nm et que la plage de vitesse de balayage est modulée entre 5 mm/sec et 3000 m/sec ; filtre de couleur utilisant la composition de résine photosensible ; procédé de fabrication du filtre de couleur ; et élément d’affichage à cristaux liquides comportant le filtre de couleur.
PCT/JP2006/312094 2005-07-29 2006-06-16 Composition de résine photosensible pour élément d’affichage à cristaux liquides, filtre de couleur l’utilisant, procédé de fabrication du filtre de couleur, et élément d’affichage à cristaux liquides Ceased WO2007013233A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007528371A JPWO2007013233A1 (ja) 2005-07-29 2006-06-16 液晶表示素子用感光性樹脂組成物、それを用いたカラーフィルター並びにその製造方法、及び、液晶表示素子

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005-222261 2005-07-29
JP2005222261 2005-07-29
JP2005-368716 2005-12-21
JP2005368716 2005-12-21

Publications (1)

Publication Number Publication Date
WO2007013233A1 true WO2007013233A1 (fr) 2007-02-01

Family

ID=37683137

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/312094 Ceased WO2007013233A1 (fr) 2005-07-29 2006-06-16 Composition de résine photosensible pour élément d’affichage à cristaux liquides, filtre de couleur l’utilisant, procédé de fabrication du filtre de couleur, et élément d’affichage à cristaux liquides

Country Status (4)

Country Link
JP (1) JPWO2007013233A1 (fr)
KR (1) KR20080030687A (fr)
TW (1) TW200712770A (fr)
WO (1) WO2007013233A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008291208A (ja) * 2007-04-27 2008-12-04 Fujifilm Corp 感光性樹脂組成物、感光性樹脂転写フイルム及びフォトスペーサーの製造方法、並びに液晶表示装置用基板及び液晶表示装置
JP2010251186A (ja) * 2009-04-17 2010-11-04 Hitachi Chem Co Ltd 導電性転写フィルム及びそれを用いた導電性パターンの形成方法
CN103052916A (zh) * 2010-08-03 2013-04-17 株式会社东进世美肯 负型感光性树脂组合物
JPWO2023136333A1 (fr) * 2022-01-14 2023-07-20

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4838403B1 (fr) * 1968-05-24 1973-11-17
JP2000098599A (ja) * 1998-09-22 2000-04-07 Fuji Photo Film Co Ltd 感光性転写材料
JP2005107191A (ja) * 2003-09-30 2005-04-21 Mitsubishi Chemicals Corp 青紫色レーザー感光性画像形成材料、青紫色レーザー感光性画像形成材及び画像形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4838403B1 (fr) * 1968-05-24 1973-11-17
JP2000098599A (ja) * 1998-09-22 2000-04-07 Fuji Photo Film Co Ltd 感光性転写材料
JP2005107191A (ja) * 2003-09-30 2005-04-21 Mitsubishi Chemicals Corp 青紫色レーザー感光性画像形成材料、青紫色レーザー感光性画像形成材及び画像形成方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008291208A (ja) * 2007-04-27 2008-12-04 Fujifilm Corp 感光性樹脂組成物、感光性樹脂転写フイルム及びフォトスペーサーの製造方法、並びに液晶表示装置用基板及び液晶表示装置
JP2010251186A (ja) * 2009-04-17 2010-11-04 Hitachi Chem Co Ltd 導電性転写フィルム及びそれを用いた導電性パターンの形成方法
CN103052916A (zh) * 2010-08-03 2013-04-17 株式会社东进世美肯 负型感光性树脂组合物
CN103052916B (zh) * 2010-08-03 2015-08-12 株式会社东进世美肯 负型感光性树脂组合物
JPWO2023136333A1 (fr) * 2022-01-14 2023-07-20

Also Published As

Publication number Publication date
KR20080030687A (ko) 2008-04-04
JPWO2007013233A1 (ja) 2009-02-05
TW200712770A (en) 2007-04-01

Similar Documents

Publication Publication Date Title
TWI530715B (zh) Production method of polarizing film
KR20080016883A (ko) 노광방법 및 노광장치
CN105093372A (zh) 滤色器、显示元件、红色像素和绿色像素
TWI375127B (en) Pattern-forming material, pattern-forming device and pattern-forming method
WO2005116774A1 (fr) Procede de formation de motif
KR20090125683A (ko) 불소 함유 화합물, 수지 조성물, 감광성 전사 재료, 분리벽과 그 형성방법, 컬러필터와 그 제조방법, 및 표시장치
WO2005116775A1 (fr) Procédé de formation de motif, procédé de fabrication de filtre couleur, filtre couleur, et affichage à cristaux liquides
WO2006059534A1 (fr) Materiau et procede de formation de motifs
WO2007013233A1 (fr) Composition de résine photosensible pour élément d’affichage à cristaux liquides, filtre de couleur l’utilisant, procédé de fabrication du filtre de couleur, et élément d’affichage à cristaux liquides
WO2006051761A1 (fr) Composition de formation de motif et matériau de formation de motif, et appareil de formation de motif et procédé de formation de motif
JP2007156011A (ja) フォトスペーサ用感光性樹脂組成物、スペーサ付き基板及びその製造方法並びに液晶表示装置
JP2008020629A (ja) パターン形成材料、並びに、パターン形成装置及びパターン形成方法
JP2007041082A (ja) 液晶表示素子用感光性樹脂組成物、それを用いたカラーフィルタ並びにその製造方法、及び、ｌｃｄ表示素子
JP2007011231A (ja) パターン形成方法、カラーフィルター付基板及び表示素子
CN101233435A (zh) 液晶显示元件用感光性树脂组合物、使用其的滤色片及其制造方法以及液晶显示元件
JP4684707B2 (ja) 液晶表示装置用構成物の製造方法
JP2007024969A (ja) セル内構造の製造方法及びセル内構造並びに表示装置
JP2007178932A (ja) カラーフィルタ用隔壁の製造方法、隔壁付基板、カラーフィルタ及びその製造方法並びに液晶表示装置
TW200530754A (en) Pattern forming process
JPWO2007074694A1 (ja) カラーフィルタ及びその製造方法、並びに液晶表示装置
KR102847519B1 (ko) 금속 패턴의 형성 방법, 및, 증착용 메탈 마스크의 제조 방법
WO2020174767A1 (fr) Procédé de fabrication de substrat à motif ajouté, procédé de fabrication de carte de circuit imprimé, procédé de fabrication de panneau tactile et stratifié
TWI896698B (zh) 金屬圖案的形成方法及蒸鍍用金屬遮罩的製造方法
JP2007041158A (ja) カラーフィルタ作成用の光硬化性樹脂着色組成物、光硬化性樹脂転写フィルム、及びそれらを用いて製造するカラーフィルタの製造方法
JP2007086692A (ja) 液晶ディスプレイ用構造材の形成方法、並びに液晶ディスプレイ用構造材形成材料、液晶表示装置用基板、液晶表示素子、及び液晶表示装置

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680027815.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007528371

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1020087004703

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 06757379

Country of ref document: EP

Kind code of ref document: A1