WO2011040083A1 - 着色感光性樹脂組成物、カラーフィルター、および液晶表示装置 - Google Patents
着色感光性樹脂組成物、カラーフィルター、および液晶表示装置 Download PDFInfo
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- WO2011040083A1 WO2011040083A1 PCT/JP2010/058307 JP2010058307W WO2011040083A1 WO 2011040083 A1 WO2011040083 A1 WO 2011040083A1 JP 2010058307 W JP2010058307 W JP 2010058307W WO 2011040083 A1 WO2011040083 A1 WO 2011040083A1
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- photosensitive resin
- resin composition
- colored photosensitive
- color filter
- colored
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Definitions
- the present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device.
- a color filter for a display device has a structure in which red, green, and blue dot images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a dark color separation wall such as a black matrix.
- a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development.
- Colored photosensitive resin liquid method (colored resist method), 4) A method of sequentially transferring images formed on a temporary support onto a final or temporary support, and 5) Preliminarily colored photosensitive resin liquid as a temporary support.
- a method of forming a colored layer by coating on the substrate, transferring the photosensitive colored layer directly onto the substrate, sequentially exposing, developing, and forming a multicolor image by repeating the number of colors is known.
- a method using an ink jet method is also known.
- the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive resin solution.
- the ink jet method has a problem that the positional accuracy of the pixels is poor, although the loss of the photosensitive resin liquid is small and the cost is advantageous.
- a color filter manufacturing method in which a black matrix is formed by a colored resist method and RGB pixels are manufactured by an inkjet method has been proposed.
- radiation-sensitive compositions containing side chain (meth) acryloyl group-containing styrene are known. According to this, even when the exposure amount is low, chipping and undercut of the pattern edge do not occur, and undissolved material does not remain at the time of development, and scum does not occur on the pattern edge, and a fine pattern can be formed.
- a colored photosensitive composition containing an acetophenone polymerization initiator is known. According to this, a black matrix having high sensitivity to light and high adhesion to a glass substrate can be formed in spite of the use of a colored substance (for example, Japanese Patent Application Laid-Open No. 2006-276173). Issue gazette).
- the present invention provides a colored photosensitive resin composition having good patternability during development and capable of forming a fine pattern, a color filter formed using the same, and a liquid crystal display device including the color filter. Is an issue.
- a colored photosensitive resin composition comprising a colorant containing a black colorant, an alkali-soluble resin, a polymerizable compound having three or more polymerizable groups, a polymerization initiator or a polymerization initiation system, and a solvent.
- a photosensitive resin layer containing the colored photosensitive resin composition is formed on the transparent substrate so as to have an optical density of 4.0, and a surface of the photosensitive resin layer facing the transparent substrate;
- the ratio W1 / W2 of the line width W1 of the first pattern formed by exposing and developing the photosensitive resin layer through the mask from the opposite surface side to the line width W2 of the mask is 0.7.
- the film thickness d2 of the first pattern obtained under exposure / development conditions in the range of 1.5 to 1.5.
- ⁇ 3> The colored photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the colorant contains at least carbon black.
- ⁇ 4> The colored photosensitive resin assembly according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerization initiator or polymerization initiation system contains at least one acylphosphine oxide-based initiator.
- ⁇ 5> The polymerizable compound according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerizable compound having three or more polymerizable groups is at least one of a trifunctional acrylic monomer and a tetrafunctional acrylic monomer. Colored photosensitive resin assemblage.
- a photosensitive transfer material in which a photosensitive resin layer formed from the colored photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5> is provided on a temporary support.
- a color filter comprising a substrate and a light-shielding portion formed using the colored photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5> and disposed on the substrate. .
- ⁇ 9> The color filter according to ⁇ 7> or ⁇ 8>, wherein the light shielding portion has an optical density of 3.5 or more.
- ⁇ 10> The color filter according to any one of ⁇ 7> to ⁇ 9>, wherein the thickness of the light shielding portion is 1.5 microns or more.
- a liquid crystal display device comprising the color filter according to any one of ⁇ 7> to ⁇ 10>.
- a colored photosensitive resin composition having good patternability during development and capable of forming a fine pattern, a color filter formed using the same, and a liquid crystal display device including the color filter. can do.
- the colored photosensitive resin composition of the present invention includes a colorant containing at least a black colorant, an alkali-soluble resin, a polymerizable compound having three or more polymerizable groups, a polymerization initiator or a polymerization initiation system, and a solvent. And a colored photosensitive resin composition. Furthermore, the photosensitive resin layer containing the colored photosensitive resin composition disposed on the transparent substrate under the following predetermined exposure / development conditions is opposite to the surface of the photosensitive resin layer facing the transparent substrate.
- the mask From the surface side, the thickness d2 of the first pattern formed by exposing and developing the photosensitive resin layer through the mask, and from the surface side of the photosensitive resin layer facing the transparent substrate, the mask A colored photosensitive resin composition having a ratio d1 / d2 of 0.3 or more with respect to the film thickness d1 of the second pattern obtained by exposing and developing the photosensitive resin layer through the transparent substrate. is there. If the ratio d1 / d2 is less than 0.3, the patterning property at the time of development becomes insufficient, and a fine pattern may not be formed. Further, for example, pixel defects may occur when a black matrix (image separation wall) is formed using the colored photosensitive resin composition.
- a photosensitive resin layer is formed on the transparent substrate using the colored photosensitive resin composition so that an optical density is 4.0, and the transparent substrate of the photosensitive resin layer is formed.
- the ratio W1 / W2 of the line width W1 of the pattern formed by exposing and developing the photosensitive resin layer through the mask from the surface opposite to the surface facing the mask to the line width W2 of the mask Is an exposure / development condition set to be in the range of 0.7 to 1.5.
- a glass, a synthetic resin film, or the like having a transmittance of 70% or more for light of 350 nm or more can be used.
- the ratio d1 / d2 is 0.3 or more, preferably 0.3 to 0.7, and exposure / development conditions in which the ratio W1 / W2 is 0.8 to 1.2. And the ratio d1 / d2 is more preferably 0.3 to 0.7.
- the ratio W1 / W2 and the ratio d1 / d2 are within such ranges, the patternability during development is further improved, fine patterns can be formed, and the occurrence of pixels over the pattern is more effectively suppressed. Is done.
- the film thickness d2 of the first pattern obtained by exposing and developing the photosensitive resin layer formed on the transparent substrate from the surface opposite to the surface facing the transparent substrate through a mask is: Above a certain exposure amount, the film thickness is almost constant and is almost equal to the set film thickness when the photosensitive resin layer is formed.
- the film thickness d1 of the second pattern obtained by exposing and developing the photosensitive resin layer formed on the transparent substrate through the mask and the transparent substrate from the side facing the transparent substrate depends on the exposure amount. When the fluctuation is large and the exposure amount is small, d1 is small, and when the exposure amount is large, d1 is large.
- the photosensitive resin layer is formed of a material having a high shielding property with an optical density of 4.0, the shielding performance in the light emission wavelength region of the exposure light source is high, so the same exposure and development conditions are used.
- D1 is smaller than d2.
- d2 becomes a substantially constant value and d1 becomes larger according to the exposure amount. Therefore, d1 defined in the present invention. / D2 also increases. In this case, not only the curing in the thickness direction proceeds, but also the curing in the width direction proceeds, so that the line width W1 of the pattern becomes large under such exposure conditions. As a result, the ratio W1 between the line width W1 of the pattern and the mask line width W2 after the pattern is formed by exposure and development through the mask from the surface opposite to the surface facing the transparent substrate of the photosensitive composition. / W2 becomes larger than 1.5, and a desired pattern cannot be obtained.
- the line width W1 of the pattern is influenced not only by the mask line width W2 and the exposure amount but also by the development conditions.
- W1 can be increased, and by strengthening the development conditions, W1 can be decreased. it can.
- d1 / d2 can be increased by adjusting the material concentration in the colored photosensitive resin composition (specifically, for example, by increasing the initiator concentration).
- the ratio d1 / d2 is larger than a predetermined value when the ratio W1 / W2 of the pattern line width W1 and the mask line width W2 is in a predetermined range. Therefore, exposure / development conditions are defined such that the ratio W1 / W2 is in the range of 0.7 to 1.5, and development is performed after exposure through a mask from the side opposite to the transparent substrate.
- the ratio d1 / d2 of the film thickness d1 of the second pattern obtained by developing after exposure through the mask from the transparent substrate side with respect to the film thickness d2 of the first pattern obtained in this manner is within a predetermined range.
- the colored curable composition of the present invention contains at least one colorant.
- the colorant used in the present invention known colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used. Specifically, pigments and dyes described in paragraph numbers [0038] to [0054] of JP-A-2005-17716, pigments described in paragraph numbers [0068] to [0072] of JP-A-2004-361447 The colorants described in paragraph numbers [0080] to [0088] of JP-A No. 2005-17521 can be preferably used.
- a black colorant is preferably included from the viewpoint of optical density.
- the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
- a mixture of pigments such as red, blue, and green can be used.
- the colorant preferably a pigment, more preferably carbon black
- This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the colorant and the pigment dispersant in an organic solvent (or vehicle) described later.
- the vehicle is a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it.
- Component organic solvent
- the disperser used for dispersing the pigment is not particularly limited.
- the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438 Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, it may be finely pulverized by frictional force by mechanical grinding described in page 310 of the document.
- the colorant used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m, from the viewpoint of dispersion stability.
- the “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, The average value of 100 is said.
- the content of the colorant in the total solid content of the colored photosensitive resin composition in the present invention is not particularly limited, but is preferably 15 to 70% by mass from the viewpoint of sufficiently shortening the development time. It is more preferably 20 to 60% by mass, and further preferably 25 to 50% by mass.
- the total solid content as used in this specification means the total amount of the non-volatile component remove
- the colored photosensitive resin composition of the present invention preferably contains at least one alkali-soluble resin. Thereby, alkali developability becomes better.
- the alkali-soluble resin hereinafter sometimes simply referred to as “binder” in the present invention, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the main chain or side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36.
- Methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc.
- the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
- the binder polymer having these polar groups may be used alone or in the form of a composition used in combination with a normal film-forming polymer, and is based on the total solid content of the colored photosensitive resin composition.
- the content is generally 20 to 50% by mass, preferably 25 to 45% by mass.
- the colored photosensitive resin composition of the present invention contains at least one polymerizable compound having three or more polymerizable groups (hereinafter sometimes simply referred to as “polymerizable compound”).
- a commonly used polymerizable compound can be used without particular limitation as long as it is a compound having three or more polymerizable groups, and is preferably a compound having 3 to 6 polymerizable groups.
- a monomer or oligomer that has three or more ethylenically unsaturated double bonds has a boiling point of 100 ° C. or higher at normal pressure, and undergoes addition polymerization upon irradiation with light is preferable.
- Such monomers and oligomers include trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa.
- urethane acrylates having three or more polymerizable groups described in JP-B-48-41708 and JP-B-50-6034; JP-B-53-24989 and JP-B-52-30490 Polyester acrylates described: Polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned.
- trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tris (2-acryloyloxyethyl) isocyanurate Is preferred.
- trifunctional or higher functional (meth) acrylate” described in JP-A No. 11-133600 can also be mentioned as a preferable example.
- the monomer or oligomer preferably has a molecular weight of 200 to 1,000.
- it preferably contains at least one selected from trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
- it contains at least one selected from (meth) acrylate and pentaerythritol tetra (meth) acrylate. These monomers or oligomers may be used alone or in combination of two or more. Moreover, you may further use together at least 1 sort (s) of the polymeric compound which has one polymeric group, and two polymeric compounds.
- the content of the polymerizable compound having three or more polymerizable groups based on the total solid content of the colored photosensitive resin composition of the present invention is generally 5 to 80% by mass, preferably 5 to 50% by mass. 10 to 40% by mass is more preferable. Within the preferable range, control of developability becomes easier. Furthermore, when the content is 5% by mass or more, the resistance to the alkaline developer in the exposed portion of the composition becomes better. Further, when it is 80% by mass or less, an increase in tackiness when the colored photosensitive resin composition is obtained is suppressed, and the handleability becomes better.
- the colored photosensitive resin composition of the present invention contains at least one of a polymerization initiator and a polymerization initiation system.
- the polymerization initiator and polymerization initiation system used in the present invention may be either a thermal polymerization initiation system using a thermal polymerization initiator or a photopolymerization initiation system using a photopolymerization initiator. From the viewpoint of the pattern shape, it is preferable to use a photopolymerization initiation system using a photopolymerization initiator.
- the photopolymerization initiator used here is a polymerization of a polymerizable compound having three or more of the aforementioned polymerizable groups by irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. It is a compound that can generate active species to be initiated, and can be appropriately selected from known photopolymerization initiators or photopolymerization initiation systems. Specific examples include trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. Compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds and the like.
- a trihalomethyl group-containing compound an acridine compound, an acetophenone compound, a biimidazole compound, an acylphosphine oxide compound, and an oxime ester compound
- a trihalomethyl group-containing compound an acridine compound, an acetophenone compound, a biimidazole compound, an acylphosphine oxide compound, and an oxime ester compound
- methyl group-containing compounds and acylphosphine oxide compounds it is more preferable to contain at least one selected from acylphosphine oxide compounds.
- Trihalomethyl group-containing compounds and acylphosphine oxide compounds are also useful in that they are versatile and inexpensive.
- trihalomethyl group-containing compounds and acylphosphine oxide compounds include trihalomethyloxazole derivatives or s-triazine derivatives substituted with a trihalomethyl group described in JP-A No. 2001-117230, US Pat. No. 4,239,850 Trihalomethyl group-containing compounds such as trihalomethyl-s-triazine compounds described in US Pat. No. 4,221,976 and trihalomethyloxadiazole compounds described in US Pat. No. 4,221,976; And acylphosphine oxide compounds described in Japanese Patent No. 15471.
- the trihalomethyl group-containing compounds include 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [ 4 '-(N, N-bis (ethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine, acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
- the polymerization initiator or the polymerization initiation system may be used alone or in combination of two or more.
- the total content of the polymerization initiator or the polymerization-initiated colored photosensitive resin composition is preferably 0.1 to 20% by mass of the total solid content (mass) of the colored photosensitive resin composition, preferably 0.5 to 10% by mass is particularly preferred.
- the total content is 0.1% by mass or more, the photocuring efficiency of the composition increases, and the exposure time can be shortened.
- the content is 20% by mass or less, it is possible to suppress the occurrence of a missing image pattern and the roughness of the pattern surface during development.
- the polymerization initiator may be used in combination with a hydrogen donor.
- the hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved.
- the “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.
- the mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor).
- the amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.
- mercaptan-based hydrogen donor examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.
- amine-based hydrogen donor examples include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
- 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.
- the hydrogen donor can be used singly or in combination of two or more.
- the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-.
- Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone.
- More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and particularly preferred combinations are 2-mercaptobenzobenzone.
- the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1 to 1: 4 is preferable, and 1: 1 to 1: 3 is more preferable.
- the total amount of the hydrogen donor in the colored photosensitive resin composition is preferably 0.1 to 20% by mass, particularly 0.5 to 10% by mass, based on the total solid content (mass) of the colored photosensitive resin composition. preferable.
- the colored photosensitive resin composition of the present invention contains at least one solvent.
- the solvent used normally can be especially used without a restriction
- an organic solvent having a boiling point of 180 ° C. to 250 ° C. can be used.
- These high-boiling solvents include diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate , Propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, ⁇ -butyrolactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, propylene Examples include glycol phenyl ether acetate and 1,3-butanediol diacetate. It is.
- the content of the solvent in the colored photosensitive resin composition of the present invention is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, and particularly preferably 20 to 85% by mass with respect to the total amount of the colored photosensitive resin composition. preferable. By setting it as the range of content of the said solvent, it is preferable at the point which can apply
- the colored photosensitive resin composition of the present invention is further known as necessary in addition to the above-described colorant, alkali-soluble resin, polymerizable compound having three or more polymerizable groups, polymerization initiator or polymerization initiator system, and solvent. Additives such as plasticizers, fillers, stabilizers, polymerization inhibitors, surfactants, adhesion promoters, and the like.
- the colored photosensitive resin composition is preferably softened or tacky at a temperature of at least 150 ° C., more preferably thermoplastic. From this viewpoint, it is preferable to further contain a compatible plasticizer.
- the colored photosensitive resin composition of the present invention 20 to 60% by mass of carbon black as a colorant and 10 to 40% by mass of a compound containing three or more (meth) acrylate groups as a polymerizable compound, polymerization initiation It is preferable to contain 0.1 to 20% by mass of a trihalomethyl group-containing compound or an acylphosphine oxide compound as a colorant, 25 to 50% by mass of carbon black as a colorant, and pentaerythritol tetraacrylate as a polymerizable compound.
- the colored photosensitive resin composition of the present invention is suitably used for forming a pattern constituting a color filter.
- it is suitable for forming a separation wall (light shielding portion, black matrix) constituting a color filter.
- the color filter of the present invention includes a substrate (hereinafter sometimes referred to as “permanent support”) and a light-shielding portion that is formed using the colored photosensitive resin composition and disposed on the substrate.
- the light shielding part preferably has an optical density of 3.5 or more, more preferably 4.0 or more.
- the light-shielding part preferably has a thickness of 1.5 ⁇ m or more, more preferably 1.7 to 2.5 ⁇ m. By providing such a light shielding portion, a color filter having good characteristics can be configured.
- the light shielding portion constitutes a separation wall of a color filter, for example.
- the separation wall of each color filter pixel in the production of a color filter for producing RGB pixels by the inkjet method is formed using the colored photosensitive resin composition.
- the image separation wall separates two or more pixel groups and is generally black, but is not limited to black.
- the separation wall is preferably formed by exposing a photosensitive resin layer formed using the colored photosensitive resin composition in a poor oxygen atmosphere and then developing the photosensitive resin layer.
- the said colored photosensitive resin composition may be apply
- a method for applying the colored photosensitive resin composition a commonly used application method can be used without any particular limitation.
- the photosensitive resin layer can be formed using a coating apparatus having a slit nozzle or a spin coater.
- the inert gas refers to a general gas such as N 2 , H 2 or CO 2 or a rare gas such as He, Ne or Ar. Among these, N 2 is preferably used because of safety, availability, and cost.
- the term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.
- the protective layer capable of blocking oxygen is, for example, a water-soluble polyvinyl ether / maleic anhydride polymer or carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824.
- the polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably 10 to 40% by mass of the solid content of the resin layer. % By mass.
- Various films can also be used as a protective layer capable of blocking oxygen.
- polyesters such as PET, polyamides such as nylon, and ethylene-vinyl acetate copolymers (EVAs) can be suitably used. These films may be stretched as necessary, and the thickness is suitably 5 to 300 ⁇ m, preferably 20 to 150 ⁇ m.
- the separation wall is produced using the following photosensitive transfer material, it can be suitably used as a layer capable of blocking oxygen provided on the temporary support described below.
- the oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this way is preferably 2000 cm 3 / (m 2 ⁇ day ⁇ atm) or less, but 100 cm 3 / (m 2 ⁇ day ⁇ atm) or less. Is more preferably 50 cm 3 / (m 2 ⁇ day ⁇ atm) or less.
- oxygen permeability is higher than 2000 cm 3 / (m 2 ⁇ day ⁇ atm), oxygen cannot be effectively blocked, and it may be difficult to control the shape of the separation wall.
- a photosensitive transfer material having at least an oxygen blocking layer and a layer made of a colored photosensitive resin composition in this order on a temporary support is permanently supported.
- the layer made of the colored photosensitive resin composition is protected by the oxygen blocking layer, it automatically becomes in an oxygen-poor atmosphere. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.
- a photosensitive transfer material having at least a layer made of a colored photosensitive resin composition on a temporary support is transferred onto the permanent support, and the permanent support, a layer made of the colored photosensitive resin composition, and a temporary support May be formed in this order, and the temporary support may be used as a “protective layer capable of blocking oxygen”. In this case, it is not necessary to provide the oxygen barrier layer, and the number of steps can be reduced.
- the above photosensitive transfer material may have a thermoplastic resin layer as necessary.
- a thermoplastic resin layer is alkali-soluble and includes at least a resin component.
- the resin component is preferably an alkali-soluble thermoplastic resin having a substantial softening point of 80 ° C. or lower.
- alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower examples include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic.
- examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.
- thermoplastic resin layer at least one of the above-mentioned thermoplastic resins can be appropriately selected and used.
- thermoplastic resins can be appropriately selected and used.
- “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council) , Issued on October 25, 1968), organic polymers having a softening point of about 80 ° C. or lower and those soluble in an alkaline aqueous solution can be used.
- a substantial softening point of 80 ° C. or lower can be obtained by adding various plasticizers compatible with the polymer substance to the organic polymer substance. It can also be used by lowering.
- these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within a range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
- preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.
- the temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance.
- a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable.
- the thickness of the temporary support is suitably 5 to 300 ⁇ m, preferably 20 to 150 ⁇ m. If the thickness is less than 5 ⁇ m, the temporary support tends to be easily broken when peeled off, and if the exposure is performed via the temporary support, the resolution tends to be lowered if the thickness exceeds 300 ⁇ m.
- a biaxially stretched polyethylene terephthalate film is particularly preferable.
- the substrate (permanent support) constituting the color filter of the present invention a metal support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.
- a photosensitive transfer material in which an oxygen blocking layer, a colored photosensitive composition layer, and a cover sheet is provided on the colored photosensitive composition layer is prepared on a temporary support.
- the surface of the exposed colored photosensitive composition layer is bonded onto a permanent support (substrate) and heated and pressurized through a laminator or the like to laminate (laminate).
- the laminator those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.
- a temporary support body peels between a temporary support body and an oxygen barrier layer, and a temporary support body is removed.
- a desired photomask for example, quartz exposure mask
- an appropriate distance between the exposure mask surface and the oxygen blocking layer for example, 200 ⁇ m
- development processing is performed using a predetermined processing solution to obtain a patterning image, and subsequently, washing processing is performed as necessary to obtain a separation wall.
- the temporary support is used as a protective layer capable of blocking oxygen
- the desired photomask for example, a quartz exposure mask
- the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 ⁇ m) and exposed.
- the temporary support is removed, and development processing is performed using a predetermined processing liquid to obtain a patterning image. Subsequently, if necessary, washing treatment is performed to obtain a separation wall.
- Examples of the light source used for light irradiation (exposure) include medium to ultrahigh pressure mercury lamps, xenon lamps, and metal halide lamps. Specifically, for example, it is performed with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 300 mJ / cm 2 ).
- a proximity type exposure machine for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
- the exposure amount can be appropriately selected (for example, 300 mJ / cm 2 ).
- the above-mentioned colored photosensitive resin composition is used to form a photosensitive resin layer having a film thickness of 1.5 to 2.5 ⁇ m and to be used in a proximity type exposure machine having an ultrahigh pressure mercury lamp in an oxygen-poor atmosphere. , 40 to 300 mJ / cm 2 , preferably a photosensitive resin layer having a film thickness of 1.7 to 2.5 ⁇ m, and a proximity type exposure machine having an ultra-high pressure mercury lamp in an oxygen-poor atmosphere. More preferably, the exposure treatment is performed at 50 to 150 mJ / cm 2 .
- developer processing is performed using a predetermined processing solution (developing solution).
- developer solution a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. Moreover, it is preferable to spray the pure water with a shower nozzle etc. before the said development, and to wet the surface of this colored photosensitive composition layer uniformly.
- alkaline substance contained in the treatment liquid examples include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, Sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, mono Examples include ethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like.
- the concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.
- water-miscible organic solvent examples include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether.
- Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone and the like are preferable.
- the concentration of the water-miscible organic solvent in the treatment liquid is preferably 0.1 to 30% by mass.
- a known surfactant can be added to the treatment liquid, and the concentration of the surfactant is preferably 0.01 to 10% by mass.
- the developer can be used as a bath solution or a spray solution.
- methods such as rubbing with a rotating brush or wet sponge in the developer can be combined.
- the liquid temperature of the developer is usually preferably from about room temperature to 40 ° C.
- the development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the unexposed area may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the separation wall shape suitable. It is also possible to put a water washing step after the development processing.
- post-curing process In the present invention, after the separation wall is formed as described above, it is preferable to perform a post-curing treatment for further fixing the shape of the separation wall.
- the means for fixing the shape of the separation wall is not particularly limited, and examples include the following. 1) After the development processing, re-exposure (hereinafter sometimes referred to as “post-exposure”) is performed. 2) After development, heat treatment (hereinafter sometimes referred to as “post-bake”) is performed at a relatively low temperature. In the present invention, it is preferable to perform at least one of post-exposure and post-bake, and it is more preferable to perform both sequentially.
- the exposure amount if 500 ⁇ 8000mJ / cm 2 it is the atmosphere, preferably 1000 ⁇ 5000mJ / cm 2, is lower than when it is under anoxic atmosphere It is also possible to expose with an exposure amount.
- the post-exposure may be performed from the side of the photosensitive resin layer opposite to the surface facing the transparent substrate, or from the surface side of the photosensitive resin layer facing the transparent substrate. It may be performed from both sides.
- the heat treatment means that the substrate on which the separation wall is formed is heated in an electric furnace, a dryer or the like, or is irradiated with an infrared lamp.
- the heating temperature is preferably 120 to 250 ° C. for 10 to 120 minutes.
- the separation wall is made water-repellent by subjecting the separation wall formed as described above to water repellency treatment.
- the ink overcomes the separation wall and suppresses inconvenience such as color mixing with the adjacent color. can do.
- Water repellent treatment includes a method of applying a water repellent material on the upper surface of the separation wall, a method of newly providing a water repellent layer, a method of imparting water repellency by plasma treatment, and a method of kneading a water repellent substance on the separation wall. And a method of imparting water repellency with a photocatalyst.
- an ink-philic treatment such as oxygen ashing may be performed in order to increase the wettability of the ink at the black matrix opening on the support.
- the matters described in JP-A-2006-154804 and the like can be suitably applied to the present invention.
- a colored liquid composition for forming RGB pixels is applied to the recesses between the separation walls formed in the developing step.
- a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable from the viewpoint of productivity.
- the ink jet method will be described later.
- the colored liquid composition applied to the recesses between the separation walls forms a colored layer.
- This colored layer becomes color pixels such as yellow (Y), red (R), green (G), and blue (B) constituting the color filter.
- the colored layer is formed by applying an inkjet ink for forming colored pixels (for example, YRGB four-color pixel pattern) to the recesses surrounded by the separation wall formed on the substrate as described above. It can be formed of a plurality of pixels of two or more colors.
- the shape of the color filter pattern is not particularly limited, and may be a general stripe shape, a lattice shape, or a delta array shape as a black matrix shape.
- the colored liquid composition is colored by a known method such as a method of thermosetting or photocuring the colored liquid composition, a method of forming a transparent image-receiving layer on a substrate in advance, and then applying a colored liquid composition. It can be a layer.
- a heating process is performed in which a colored liquid composition is applied to the recesses between the separation walls to form each pixel, and then a heating process (so-called baking process) is performed. That is, the substrate to which the colored liquid composition is applied is heated in an electric furnace, a dryer or the like, or infrared rays are irradiated with an infrared lamp.
- the heating temperature and time depend on the composition of the colored liquid composition and the thickness of the formed layer, but generally from about 120 ° C. to about 250 ° C. from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is preferred to heat at about 10 minutes to about 120 minutes.
- Examples of the ink jet method used in the present invention include a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is intermittently heated by using its foaming.
- Various methods such as a method of injecting the ink can be employed.
- the ink used may be oily or water-based.
- the coloring material contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability.
- a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063]) or JP-A-10-195358 [0009], which is used for producing a known color filter, is used.
- the ink-jet composition described in [0026] can also be used.
- thermosetting resins can be used without particular limitation as the component that is cured by heating.
- a thermosetting ink for a color filter containing at least a binder and a bifunctional to trifunctional epoxy group-containing monomer can also be used as a preferable one.
- cured with an energy ray what added the photoinitiator to the acrylate derivative or the methacrylate derivative can be illustrated, for example.
- those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable.
- These acrylate derivatives and methacrylate derivatives are preferably water-soluble.
- even water-insoluble ones can be used after being emulsified.
- the colored photosensitive resin composition containing a colorant such as a pigment described in the section of the colored photosensitive resin composition can be used as a suitable one.
- the color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form a three-color filter by applying RGB three-color ink.
- This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.
- an overcoat layer can be provided on the entire surface of the color filter in order to improve resistance.
- the overcoat layer protects the solidified layer of each pixel (for example, R, G, B) and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.
- Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually composed mainly of an acrylic resin and has excellent adhesion, so that the acrylic resin composition Things are desirable.
- Examples of the overcoat layer include those described in JP-A 2003-287618, paragraphs 0018 to 0028, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.
- the display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device.
- a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device.
- Display Devices (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.) Issue)).
- a liquid crystal display device is particularly preferable.
- the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device.
- the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of “EL, PDP, LCD Display -Technology and Latest Trends in the Market- (Toray Research Center Research Division 2001)”.
- the liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter.
- the color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)” and “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi Co., Ltd.) Fuji Chimera Research Institute, published in 2003) ”.
- the color filter of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile phones and other portable terminals, digital cameras, car navigation systems and the like.
- Example 1 [Preparation of colored photosensitive resin composition] (Preparation of K pigment dispersion 1) Carbon black, a dispersant, a polymer and a solvent were mixed so that the composition of the following K pigment dispersion 1 was obtained, and a K pigment dispersion 1 was obtained using a three roll and bead mill.
- the black composition K1 (colored photosensitive resin composition) was first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate (MMPGAc) listed in Table 1 at a temperature of 24 ° C. ( ⁇ 2 ° C.). Mix and stir at 150 RPM for 10 minutes, then weigh out the amounts of methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, monomer liquid 1, polymerization initiator 1 and surfactant 1 listed in Table 1 at a temperature of 25 ° C. ( ( ⁇ 2 ° C.) in this order, and stirring at 150 RPM for 30 minutes at a temperature of 24 ° C. ( ⁇ 2 ° C.).
- the quantity described in Table 1 is the number of parts based on mass. Each component has the following composition in detail.
- the alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water.
- the substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
- the black composition K1 obtained above with a glass substrate coater manufactured by FS Japan Co., Ltd., trade name: MH-1600 having a slit-like nozzle. was applied.
- black photosensitive layer (hereinafter sometimes referred to as “black photosensitive layer”) K1 having a film thickness of 2.33 ⁇ m and an optical density of 4.0.
- a proximity type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd. having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the black photosensitive layer K1 The distance was set to 200 ⁇ m, and pattern exposure was performed at an exposure amount of 300 mJ / cm 2 from the black photosensitive layer K1 side in a nitrogen atmosphere.
- KOH developer KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film) Electronics Materials Co., Ltd.
- a KOH developer KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film) Electronics Materials Co., Ltd.
- the residue was removed by spraying to obtain a patterning image.
- the pattern line width (W1) with respect to the mask line width of 12.0 ⁇ m (W2) was 13.7 ⁇ m as a result of measurement with a fine line width measuring device (CP-30; manufactured by Softworks).
- the film thickness d2 measured with a stylus type film thickness meter (P-10; manufactured by Tencor Instrument) was 2.33 ⁇ m.
- the exposure amount is 2500 mJ / cm 2 from both sides of the surface of the black photosensitive layer K1 opposite to the surface facing the substrate and the surface of the black photosensitive layer K1 facing the substrate.
- Post-exposure was performed, and a post-bake treatment at 240 ° C. for 50 minutes was further performed to obtain a substrate on which a separation wall having an optical density of 3.9 and a thickness (d2) of 2.0 ⁇ m was formed.
- the substrate and the separation wall are separated from the back surface (the surface on which the separation wall is not formed) of the substrate on which the separation wall is formed with an exposure amount of 110 mJ / cm 2 (38 mW / cm 2 ⁇ 2.9 seconds). Exposed through. After immersing and shaking in an inorganic alkaline developer (Hoechst Japan, AZ400K developer, 1: 4) for 80 seconds, rinse treatment was performed in pure water for 30 to 60 seconds. Next, a water repellent resin layer was formed on the separation wall. As a result, a surface energy difference was provided between the inside and outside of the pixel (the concave portion surrounded by the separation wall and the separation wall).
- the surface energy inside and outside the pixel after forming the water repellent resin layer is 10 to 15 dyne / cm outside the pixel (on the resin layer), and around 55 dyne / cm inside the pixel (on the glass substrate, surrounded by the separation wall). there were.
- a pigment, a polymer dispersant and a solvent were mixed so as to have the following composition, and a pigment dispersion was obtained using a three roll and a bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials are added little by little to obtain a colored liquid composition for red (R) pixels (hereinafter sometimes referred to as “colored ink composition for pixels”). Prepared.
- a green (G) pixel colored ink composition was prepared in the same manner as the red pixel colored ink composition except that the same amount of pigment green 36 was used.
- a blue (B) pixel colored ink composition was prepared in the same manner as the red pixel colored ink composition except that the same amount of CI Pigment Blue 15: 6 was used.
- Pixel defects in the obtained color filter were evaluated as follows. The number of defective pixels is calculated by observing the presence or absence of defects such as blurring, protrusion, and color mixing with adjacent pixels using an optical microscope for 2500 picture elements with a total of 3 pixels, one for each of RGB of the color filter. Evaluation was made according to the following evaluation criteria. The results are shown in Table 1. -Evaluation criteria- A: 0 to 2 defects B: Number of defects 3-5 C: 6 to 10 defects D: 11-25 defects E: 26 or more defects
- a transparent electrode made of ITO Indium Tin Oxide
- ITO Indium Tin Oxide
- a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.
- the ITO resistance of this color filter was measured ("Loresta” manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), and a very low value of 12 ⁇ / ⁇ was shown.
- a photospacer was provided in a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon. Then, after printing an epoxy resin sealant at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter and dropping the PVA mode liquid crystal and bonding it to the counter substrate The bonded substrate was heat treated to cure the sealant.
- Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained.
- a backlight of a cold cathode tube was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to constitute a liquid crystal display device.
- the obtained liquid crystal display device had no problem in brightness and was excellent in display characteristics.
- the luminance (Y) was measured using a color luminance meter BM-5A (manufactured by Topcon Corporation), and the brightness was evaluated according to the following evaluation criteria.
- thermoplastic film layer having a dry film thickness of 15.1 ⁇ m, the intermediate layer having a dry film thickness of 1.6 ⁇ m, and the dry film thickness so that the optical density is 4.0 are formed on the temporary support.
- a 2.2 ⁇ m black photosensitive layer was provided, and finally a protective film (12 ⁇ m thick polypropylene film) was pressure-bonded.
- a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) black photosensitive layer were integrated was prepared, and the sample name was black photosensitive transfer material K1.
- a non-alkali glass substrate is washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering.
- silane coupling solution N- ⁇ (aminoethyl) A 0.3% aqueous solution of ⁇ -aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
- KBM603 0.3% aqueous solution of ⁇ -aminopropyltrimethoxysilane
- the cover film is removed from the black photosensitive transfer material K1 produced by the above manufacturing method on the obtained silane coupling treated glass substrate, and the surface of the black photosensitive layer exposed after the removal and the silane coupling treated glass substrate
- the substrates are heated so as to be in contact with each other, and a laminator (manufactured by Hitachi Industries (Lamic II type)) is used to heat the substrate at 100 ° C. for 2 minutes.
- the rubber roller temperature is 130 ° C.
- the linear pressure is 100 N / cm
- Lamination was performed at a conveyance speed of 2.2 m / min.
- the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.
- the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp.
- the distance between the surface and the black photosensitive resin composition layer was set to 200 ⁇ m, and pattern exposure was performed at an exposure amount of 70 mJ / cm 2 .
- triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water).
- the mixture was diluted to 30) at 20 ° C. for 20 seconds with a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer.
- pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
- a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) is diluted 5 times with pure water (mixed with 1 part of T-CD1 and 4 parts of pure water).
- the shower pressure was set to 0.1 MPa at 30 ° C. using a diluted solution), developed for 30 seconds, and washed with pure water.
- the pattern line width (W1) with respect to the mask line width of 12.0 ⁇ m (W2) was 13.3 ⁇ m as a result of measurement with a fine line width measuring device (CP-30; manufactured by Softworks).
- the film thickness d2 measured with a stylus type film thickness meter (P-10; manufactured by Tencor Instrument) was 2.33 ⁇ m.
- post-exposure was performed in the atmosphere at an exposure amount of 2000 mJ / cm 2 , and further post-baking treatment was performed at 240 ° C. for 50 minutes to form a separation wall having an optical density of 3.9 and a film thickness of 2.0 ⁇ m.
- a substrate was obtained.
- the black photosensitive layer K1 having a thickness of 2.33 ⁇ m was formed in the same manner as described above, after the exposure and development were performed in the same manner as described above except that the substrate was set so that the black photosensitive layer K1 was exposed from the substrate side. As a result of measuring the film thickness d1 of the obtained patterning image, it was 0.71 ⁇ m.
- the R, G, and B pixels were formed by the inkjet method in the same manner as in Example 1 except that the substrate having the separation wall formed as described above was used.
- the black matrix and each pixel were completely cured by baking for 60 minutes.
- Example 2 an ITO transparent electrode was formed on the R pixel, G pixel, B pixel, and black matrix, and an alignment film made of a photospacer and polyimide was provided. After that, a sealant was printed, liquid crystal was dropped, bonded to the counter substrate, and heat-treated to produce a liquid crystal cell. A polarizing plate was pasted on both sides to constitute a backlight, and a liquid crystal display device was constructed. The obtained liquid crystal display device had no problem in brightness and was excellent in display characteristics. Further, the brightness of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.
- Examples 3 to 6 Instead of the black composition K1 in Example 2, black compositions K3 to K6 were prepared so as to have the compositions described in Examples 3 to 6 in Table 1, respectively. Using this, black transfer materials K3 to K6 were respectively produced in the same manner as in Example 2, and a separation wall was formed on the substrate in the same manner as in Example 2 except that this was used. W1, d1, and d2 were obtained. Further, a color filter was produced in the same manner as in Example 2 except that the substrate obtained above was used, and then a liquid crystal display device was produced. Table 1 also shows the evaluation results of the pixel defects of the color filter and the brightness of the liquid crystal display device evaluated in the same manner as in Example 1.
- Example 6 Hanarega instead of the wall during production of the exposure 70 mJ / cm 2, exposure dose 40mJ / cm 2, 150mJ / cm 2 and with other than the in Hanarega wall to the substrate as in Example 6 And W1, d1, and d2 were obtained. Further, a color filter was produced in the same manner as in Example 6 except that the substrate obtained above was used, and then a liquid crystal display device was produced. Table 1 also shows the evaluation results of the pixel defects of the color filter and the brightness of the liquid crystal display device evaluated in the same manner as in Example 1.
- Examples 9 to 11 Instead of the black composition K1 in Example 2, black compositions K9 to K11 were prepared so as to have the compositions described in Examples 9 to 11 in Table 1, respectively. Using this, black transfer materials K9 to K11 were respectively produced in the same manner as in Example 2, and a separation wall was formed on the substrate in the same manner as in Example 2 except that this was used. W1, d1, and d2 were obtained. Further, a color filter was produced in the same manner as in Example 2 except that the substrate obtained above was used, and then a liquid crystal display device was produced. Table 1 also shows the evaluation results of the pixel defects of the color filter and the brightness of the liquid crystal display device evaluated in the same manner as in Example 1.
- R pigment dispersion 1 in Table 1 was obtained by mixing a pigment, a polymer, and a solvent so as to have the following composition, and using a three-roll and bead mill, R pigment dispersion 1 was obtained.
- Polymer: 12% (Random copolymer of benzyl methacrylate / methacrylic acid 72/28 molar ratio, molecular weight 37,000)
- a black composition K21 was prepared so as to have the composition described in Comparative Example 1 of Table 1.
- a black transfer material K21 was produced in the same manner as in Example 2.
- Hanarega wall during production of the exposure 70 mJ / cm 2 in Example 2
- W1 , D1 and d2 were obtained.
- a color filter was produced in the same manner as in Example 2 except that the substrate obtained above was used, and then a liquid crystal display device was produced.
- Table 1 also shows the evaluation results of the pixel defects of the color filter and the brightness of the liquid crystal display device evaluated in the same manner as in Example 1.
- MMPGAc represents propylene glycol monomethyl ether acetate.
- the monomer liquid 2 is a propylene glycol monomethyl ether acetate solution (76%) of DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.).
- the polymerization initiator 2 represents Irgacure 819 (manufactured by Ciba Japan)
- the polymerization initiator 3 represents Irgacure 379 (manufactured by Ciba Japan)
- the polymerization initiator 4 represents Irgacure OXE01 (manufactured by Ciba Japan).
- Additive 1 is NBCA (10-n-butyl-2-chloroacridone, manufactured by Kurokin Kasei), and Additive 2 is EAB-F (photopolymerization initiation assistant, Hodogaya Chemical Co., Ltd.) )))).
- the colored photosensitive resin composition of the present invention it was possible to form pixels without color mixing with high positional accuracy and to manufacture a color filter and a liquid crystal display device with high efficiency.
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Abstract
Description
また、アセトフェノン系重合開始剤を含む着色感光性組成物が知られている。これによれば、着色物質を用いているにも関わらず、光に対して高感度で、かつガラス基板への密着性が高いブラックマトリックスが形成できるとされている(例えば、特開2006-276173号公報参照)。
本発明は、現像時のパターニング性がよく、微細パターンの形成が可能な着色感光性樹脂組成物、およびこれを用いて形成されるカラーフィルター、ならびに該カラーフィルターを備える液晶表示装置を提供することを課題とする。
<1> 黒色の色材を含む着色剤と、アルカリ可溶性樹脂と、重合性基を3つ以上有する重合性化合物と、重合開始剤または重合開始系と、溶剤と、を含む着色感光性樹脂組成物であって、透明基板上に光学濃度が4.0となるように前記着色感光性樹脂組成物を含む感光性樹脂層を形成し、前記感光性樹脂層の前記透明基板に対向する面とは反対の面側から、マスクを介して前記感光性樹脂層を露光・現像処理して形成される第1のパターンの線幅W1の前記マスクの線幅W2に対する比W1/W2が0.7から1.5の範囲となる露光・現像条件で得られる前記第1のパターンの膜厚d2と、前記感光性樹脂層の前記透明基板に対向する面側から、マスクと前記透明基板とを介して、前記W1/W2が0.7から1.5の範囲となる露光・現像条件で、前記感光性樹脂層を露光・現像処理して得られる第2のパターンの膜厚d1との比d1/d2が0.3以上である着色感光性樹脂組成物。
<2> 前記W1/W2が0.8から1.2の範囲となる露光・現像条件における前記d1/d2が、0.3から0.7の範囲である前記<1>に記載の着色感光性樹脂組成物。
<4> 前記重合開始剤または重合開始系は、少なくとも1種のアシルホスフィンオキサイド系開始剤を含有する前記<1>~<3>のいずれか1項に記載の着色感光性樹脂組生物。
<5> 前記重合性基を3つ以上有する重合性化合物は、3官能のアクリルモノマーおよび4官能のアクリルモノマーの少なくとも1種である前記<1>~<4>のいずれか1項に記載の着色感光性樹脂組生物。
<7> 基板と、前記<1>~<5>のいずれか1項に記載の着色感光性樹脂組成物を用いて形成されると共に前記基板上に配置された遮光部と、を備えるカラーフィルター。
<8> 前記遮光部は、前記<6>に記載の感光性転写材料を用いて形成された前記<7>に記載のカラーフィルター。
<9> 前記遮光部の光学濃度が3.5以上である前記<7>または<8>に記載のカラーフィルター。
<10> 前記遮光部の膜厚が1.5ミクロン以上である前記<7>~<9>のいずれか1項に記載のカラーフィルター。
<11> 前記<7>~<10>のいずれか1項に記載のカラーフィルターを備える液晶表示装置。
本発明の着色感光性樹脂組成物は、黒色の色材を少なくとも含む着色剤と、アルカリ可溶性樹脂と、重合性基を3つ以上有する重合性化合物と、重合開始剤または重合開始系と、溶剤と、を含む着色感光性樹脂組成物である。さらに、下記所定の露光・現像条件で、透明基板上に配置された前記着色感光性樹脂組成物を含む感光性樹脂層を、前記感光性樹脂層の前記透明基板に対向する面とは反対の面側から、マスクを介して前記感光性樹脂層を露光・現像処理して形成される第1のパターンの膜厚d2と、前記感光性樹脂層の前記透明基板に対向する面側から、マスクと前記透明基板とを介して前記感光性樹脂層を露光・現像処理して得られる第2のパターンの膜厚d1との比d1/d2が0.3以上となる着色感光性樹脂組成物である。
前記比d1/d2が0.3未満では、現像時の現像時のパターニング性が不充分になり、微細パターンを形成できない場合がある。また例えば、前記着色感光性樹脂組成物を用いてブラックマトリックス(離画壁)を形成するときに画素欠けが発生する場合がある。
また、所定の露光・現像条件を設定する際に用いる前記透明基板としては、350nm以上の光に対する透過率が70%以上であるガラス、合成樹脂フィルム等を使用することができる。
一方、着色感光性樹脂組成物中の素材濃度を調整すること(具体的には例えば、開始剤濃度を高くするなど)により、d1/d2を大きくすることができる。しかし、上記同様にW1が大きくなる傾向にあるのに加えて、パターン形成後のベーク時の膜減りが大きく、基板汚染を生じやすくなる。そのため、着色感光性樹脂組成物中の素材濃度を調整することだけで、所望のW1/W2およびd1/d2を達成することは困難である。
本発明の着色硬化性組成物は、着色剤の少なくとも1種を含む。本発明に用いる着色剤としては、公知の着色剤(有機顔料、無機顔料、染料等)を好適に用いることができる。具体的には、特開2005-17716号公報の段落番号[0038]~[0054]に記載の顔料及び染料、特開2004-361447号公報の段落番号[0068]~[0072]に記載の顔料、特開2005-17521号公報の段落番号[0080]~[0088]に記載の着色剤等を好適に用いることができる。
尚、本発明においては、黒色着色剤の他に、赤、青、緑色等の顔料の混合物等を用いることができる。
前記顔料を分散させる際に使用する分散機としては、特に制限はなく、例えば、朝倉邦造著、「顔料の事典」、第一版、朝倉書店、2000年、438項に記載されているニーダー、ロールミル、アトライダー、スーパーミル、ディゾルバ、ホモミキサー、サンドミル等の公知の分散機が挙げられる。更に該文献310頁記載の機械的摩砕により、摩擦力を利用して微粉砕してもよい。
尚、本明細書でいう全固形分とは着色感光性樹脂組成物から溶剤を除いた不揮発性成分の総量を意味する。
本発明の着色感光性樹脂組成物は、アルカリ可溶性樹脂の少なくとも1種を含むことが好ましい。これによりアルカリ現像性がより良好になる。
本発明におけるアルカリ可溶性樹脂(以下、単に「バインダー」ということがある)としては、主鎖または側鎖にカルボン酸基やカルボン酸塩基などの極性基を有するポリマーが好ましい。その例としては、特開昭59-44615号公報、特公昭54-34327号公報、特公昭58-12577号公報、特公昭54-25957号公報、特開昭59-53836号公報及び特開昭59-71048号公報に記載されているようなメタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等を挙げることができる。また側鎖にカルボン酸基を有するセルロース誘導体も挙げることができ、またこの他にも、水酸基を有するポリマーに環状酸無水物を付加したものも好ましく使用することができる。
また、特に好ましい例として、米国特許第4139391号明細書に記載のベンジル(メタ)アクリレートと(メタ)アクリル酸との共重合体や、ベンジル(メタ)アクリレートと(メタ)アクリル酸と他のモノマーとの多元共重合体を挙げることができる。これらの極性基を有するバインダーポリマーは、単独で用いてもよく、あるいは通常の膜形成性のポリマーと併用する組成物の状態で使用してもよく、着色感光性樹脂組成物の全固形分に対する含有量は20~50質量%が一般的であり、25~45質量%が好ましい。
本発明の着色感光性樹脂組成物は、重合性基を3つ以上有する重合性化合物(以下、単に「重合性化合物」ということがある)の少なくとも1種を含有する。
前記重合性化合物は、重合性基を3つ以上有する化合物であれば特に制限なく通常用いられる重合性化合物を用いることができ、重合性基を3~6つ有する化合物であることが好ましい。中でも、エチレン性不飽和二重結合を3つ以上有し、沸点が常圧で100℃以上の化合物であり、光の照射によって付加重合するモノマー又はオリゴマーであることが好ましい。
更に特公昭48-41708号公報、特公昭50-6034号公報に記載されている重合性基を3つ以上有するウレタンアクリレート類;特公昭53-24989号公報、及び特公昭52-30490号公報に記載されているポリエステルアクリレート類;エポキシ樹脂と(メタ)アクリル酸の反応生成物であるエポキシアクリレート類等の多官能アクリレー卜やメタクリレートを挙げることができる。
具体的には、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、およびジペンタエリスリトールヘキサ(メタ)アクリレートから選ばれる少なくとも1種を含むことが好ましく、トリメチロールプロパントリ(メタ)アクリレート、およびペンタエリスリトールテトラ(メタ)アクリレートから選ばれる少なくとも1種を含むことがより好ましい。
これらのモノマー又はオリゴマーは、1種単独でも、2種類以上を混合して用いてもよい。また、重合性基を1つ有する重合性化合物および2つ有する重合性化合物の少なくとも1種をさらに併用してもよい。
本発明の着色感光性樹脂組成物は、重合開始剤および重合開始系の少なくとも1種を含む。前記本発明に用いる重合開始剤および重合開始系としては、熱重合開始剤を用いる熱重合開始系および光重合開始剤を用いる光重合開始系のいずれであってもよいが、本発明では硬化後のパターン形状の観点から、光重合開始剤を用いる光重合開始系を用いることが好ましい。
また前記水素供与体の着色感光性樹脂組成物における総量としては、着色感光性樹脂組成物の全固形分(質量)の0.1~20質量%が好ましく、0.5~10質量%が特に好ましい。
本発明の着色感光性樹脂組成物は、溶剤の少なくとも1種を含む。前記溶剤としては、通常用いられる溶剤を特に制限なく用いることができる。具体的には例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類等が挙げられる。
また、US2005/282073A1号明細書の段落番号[0054][0055]に記載のSolventと同様のメチルエチルケトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノン、シクロヘキサノール、メチルイソブチルケトン、乳酸エチル、及び乳酸メチル等も本発明においても好適に用いることができる。
これら溶剤のうち、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、ジエチレングリコールモノエチルエーテルアセテート(エチルカルビトールアセテート)、ジエチレングリコールモノブチルエーテルアセテート(ブチルカルビトールアセテート)、プロピレングリコールメチルエーテルアセテート、及びメチルエチルケトン等が本発明における溶剤として好ましく用いられる。これらの溶剤は、1種単独でもあるいは2種以上組み合わせて用いてもよい。
また前記着色感光性樹脂組成物は少なくとも150℃以下の温度で軟化もしくは粘着性になることが好ましく、熱可塑性であることがより好ましい。かかる観点からは、相溶性の良い可塑剤をさらに含有することが好ましい。
本発明のカラーフィルターは、基板(以下、「永久支持体」ということがある)と、前記着色感光性樹脂組成物を用いて形成され、前記基板上に配置された遮光部とを備える。本発明において前記遮光部は、その光学濃度が3.5以上であることが好ましく、4.0以上であることがより好ましい。また前記遮光部は、その膜厚が1.5μm以上であることが好ましく、1.7~2.5μmであることがより好ましい。かかる遮光部を備えることにより、良好な特性を有するカラーフィルターを構成することができる。
本発明において前記遮光部は、例えばカラーフィルターの離画壁を構成する。
RGB画素をインクジェット法で作製するカラーフィルター製造におけるカラーフィルター各画素の離画壁は、前記着色感光性樹脂組成物を用いて形成されることが好ましい。離画壁は、2以上の画素群を離画するものであり、一般には黒であることが多いが、黒に限定されるものではない。
離画壁は、前記着色感光性樹脂組成物を用いて形成した感光性樹脂層を貧酸素雰囲気下にて露光し、その後現像することにより形成することが好ましい。
前記着色感光性樹脂組成物を塗布する方法としては、通常用いられる塗布方法を特に制限なく用いることができる。例えば、スリットノズルを備えた塗布装置やスピンコーターを用いて感光性樹脂層を形成することができる。
前記減圧下とは500hPa以下、好ましくは100hPa以下の状態を指す。
また、前記酸素を遮断しうる保護層とは、例えば、特開昭46-2121号や特公昭56-40824号の各公報に記載の、ポリビニルエーテル/無水マレイン酸重合体、カルボキシアルキルセルロースの水溶性塩、水溶性セルロースエーテル類、カルボキシアルキル澱粉の水溶性塩、ポリビニルアルコール、ポリビニルピロリドン、各種のポリアクリルアミド類、各種の水溶性ポリアミド、ポリアクリル酸の水溶性塩、ゼラチン、エチレンオキサイド重合体、各種の澱粉およびその類似物からなる群の水溶性塩、スチレン/マレイン酸の共重合体、マレイネート樹脂、及びこれらの2種以上の組合せ等を含む樹脂層が挙げられる。
これらの中でも特に好ましいのは、ポリビニルアルコールとポリビニルピロリドンの組合せである。さらにポリビニルアルコールは鹸化率が80%以上であるものが好ましく、ポリビニルピロリドンの含有量は樹脂層固形分の1~75質量%が好ましく、より好ましくは1~50質量%、更に好ましくは10~40質量%である。
また、離画壁を下記感光性転写材料を用いて作製する場合、下記に記載の仮支持体上に設けられた酸素を遮断しうる層として好適に用いることも可能である。
かかる離画壁を容易且つ低コストで実現するものとして、仮支持体上に少なくとも酸素遮断層と着色感光性樹脂組成物からなる層とを、この順に有してなる感光性転写材料を永久支持体上に転写して、永久支持体、着色感光性樹脂組成物からなる層、酸素遮断層をこの順に形成して使用するという手法がある。このような材料を用いた場合、着色感光性樹脂組成物からなる層は酸素遮断層に保護されるため自動的に貧酸素雰囲気下となる。そのため露光工程を不活性ガス下や減圧下で行う必要がないため、現状の工程をそのまま利用できる利点がある。また、仮支持体上に少なくとも着色感光性樹脂組成物からなる層を有する感光性転写材料を永久支持体上に転写して、永久支持体、着色感光性樹脂組成物からなる層、仮支持体をこの順に形成して、該仮支持体を「酸素を遮断しうる保護層」として用いてもよい。この場合は、上記酸素遮断層を設ける必要がなく、工程数を削減することが可能である。
本発明のカラーフィルターを構成する基板(永久支持体)としては、金属性支持体、金属張り合わせ支持体、ガラス、セラミック、合成樹脂フィルム等を使用することができる。特に好ましくは、透明性で寸度安定性の良好なガラスや合成樹脂フィルムが挙げられる。
以下、前記感光性転写材料を用いて基板上に離画壁を形成する場合の一例について説明する。
仮支持体上に、酸素遮断層、着色感光性組成物層、更に該着色感光性組成物層上にカバーシートが設けられた感光性転写材料を用意する。
まず、カバーシートを剥離除去した後、露出した着色感光性組成物層の表面を永久支持体(基板)上に貼り合わせ、ラミネーター等を通して加熱、加圧して積層する(積層体)。ラミネーターには、従来公知のラミネーター、真空ラミネーター等の中から適宜選択したものが使用でき、より生産性を高めるには、オートカットラミネーターも使用可能である。
続いて、仮支持体除去後の除去面の上方に所望のフォトマスク(例えば、石英露光マスク)を垂直に立てた状態で、露光マスク面と該酸素遮断層の間の距離を適宜(例えば、200μm)に設定し、露光する。
次いで、露光後、所定の処理液を用いて現像処理して、パターニング画像を得て、引き続き必要に応じて、水洗処理して、離画壁を得る。
また、仮支持体を酸素を遮断しうる保護層として用いる場合は、仮支持体を残したまま(剥離せずに)、該仮支持体の上方に所望のフォトマスク(例えば、石英露光マスク)を垂直に立てた状態で、露光マスク面と該仮支持体の間の距離を適宜(例えば、200μm)に設定し、露光する。
次いで、仮支持体を除去し、所定の処理液を用いて現像処理して、パターニング画像を得て、引き続き必要に応じて、水洗処理して、離画壁を得る。
また前記現像の前には、純水をシャワーノズル等にて噴霧して、該着色感光性組成物層の表面を均一に湿らせることが好ましい。
アルカリ性物質の濃度は、0.01~30質量%が好ましく、pHは8~14が好ましい。
水と混和性の有機溶剤の処理液中の濃度は0.1~30質量%が好ましい。
更に処理液には、公知の界面活性剤を添加することもでき、該界面活性剤の濃度としては0.01~10質量%が好ましい。
感光性樹脂層の未硬化部分を除去する場合、現像液中で回転ブラシや湿潤スポンジで擦るなどの方法を組合わせることができる。
また現像液の液温度は、通常室温付近から40℃が好ましい。
現像時間は、感光性樹脂層の組成、現像液のアルカリ性や温度、有機溶剤を添加する場合にはその種類と濃度等に依るが、通常10秒~2分程度である。短すぎると非露光部の現像が不充分となることがあり、長すぎると露光部もエッチングされることがある。いずれの場合にも、離画壁形状を好適なものとすることが困難となる。
現像処理の後に水洗工程を入れることも可能である。
本発明においては、上記のようにして離画壁を形成した後、離画壁の形状をさらに固定化する後硬化処理を行うことが好ましい。離画壁の形状を固定化する手段としては特に限定されないが、以下のようなものが挙げられる。
1)現像処理後、再露光(以下、「ポスト露光」と呼ぶことがある)を行う。
2)現像後、比較的低い温度で加熱処理(以下、「ポストベーク」ということがある)を行う。
本発明においては、ポスト露光およびポストベークの少なくとも一方を行うことが好ましく、両方を順次行うことがより好ましい。
温度を120℃以上とすることで離画壁の硬化が効果的に進行し、充分な耐溶剤性、耐アルカリ性、を付与することができる。
本発明においては、上記のようにして形成した離画壁に撥水処理を施す事で該離画壁の少なくとも一部が撥水性を帯びた状態とすることが好ましい。これにより、その後にインクジェットなどの方法で、着色液体組成物の液滴を該離画壁間に付与した時に、インクが該離画壁を乗り越えて、隣の色と混色するなどの不都合を抑制することができる。
該撥水処理の前、または後に、支持体上のブラックマトリックス開口部でのインクの濡れ広がり性を上げるために酸素アッシング等の親インク処理を施しても良い。
尚、撥水処理の詳細については、特開2006-154804号公報等に記載の事項を本発明においても好適に適用することができる。
ついで、上記現像工程にて形成された離画壁間の凹部に対し、RGB各画素を形成する為の着色液体組成物を付与する。着色液体組成物を離画壁空隙に付与する方法としては、インクジェット法やストライプギーサー塗布法など公知のものを使用することができ、インクジェット法が生産性の点から好ましい。インクジェット法については後述する。
着色層の形成は、既述のようにして基板上に形成された離画壁で取り囲まれた凹部に、着色画素(例えばYRGB4色の画素パターン)を形成するためのインクジェットインクを付与して、2色以上の複数の画素で構成されるように形成することができる。
カラーフィルタパターンの形状については、特に限定はなく、ブラックマトリックス形状として一般的なストライプ状であっても、格子状であっても、さらにはデルタ配列状であってもよい。
加熱の温度及び時間は、着色液体組成物の組成や形成された層の厚みに依存するが、一般に充分な耐溶剤性、耐アルカリ性、及び紫外線吸光度を獲得する観点から、約120℃~約250℃で約10分~約120分間加熱することが好ましい。
本発明に用いるインクジェット法としては、帯電したインクを連続的に噴射し電場によって制御する方法、圧電素子を用いて間欠的にインクを噴射する方法、インクを加熱しその発泡を利用して間欠的に噴射する方法等、各種の方法を採用できる。
用いるインクは油性、水性であっても使用できる。
また、そのインクに含まれる着色材は染料、顔料ともに使用でき、耐久性の面からは顔料の使用がより好ましい。
また、公知のカラーフィルター作製に用いる、塗布方式の着色インク(着色樹脂組成物、例えば、特開2005-3861号公報[0034]~[0063]記載)や、特開平10-195358号公報[0009]~[0026]に記載のインクジェット用組成物を使用することもできる。
加熱によって硬化する成分としては各種の熱硬化性樹脂を特に制限なく用いることができる。本発明においては、熱硬化性樹脂に加えて、少なくともバインダー、及び、2官能ないし3官能のエポキシ基含有モノマーを含有するカラーフィルター用熱硬化性インクも好適なものとして用いることができる。
またエネルギー線によって硬化する成分としては例えばアクリレート誘導体又はメタクリレート誘導体に光反応開始剤を添加したものを例示できる。特に耐熱性を考慮してアクリロイル基、メタクリロイル基を分子内に複数有するものがより好ましい。これらのアクリレート誘導体、メタクリレート誘導体は水溶性のものが好ましく使用できる。また、水に難溶性のものでもエマルション化するなどして使用できる。この場合、上記着色感光性樹脂組成物の項で挙げた、顔料などの着色剤を含有させた着色感光性樹脂組成物を、好適なものとして用いることができる。
このカラーフィルターは、液晶表示素子、電気泳動表示素子、エレクトロクロミック表示素子、PLZT等と組合せて表示素子として用いられる。
またカラーカメラやその他のカラーフィルターを用いる用途にも使用できる。
カラーフィルターの作製後、カラーフィルター上の全面に耐性向上のためにオーバーコート層を設けることもできる。オーバーコート層は、各画素(例えば、R、G、B)の固化層を保護するとともに、表面を平坦にすることができるが、工程数が増えるという観点から、設けないことが好ましい。
中でも、可視光領域での透明性で優れており、また、カラーフィルター用光硬化性組成物の樹脂成分が通常アクリル系樹脂を主成分としており、密着性に優れていることからアクリル系樹脂組成物が望ましい。
オーバーコート層の例として、特開2003-287618号公報の段落番号0018~0028に記載のものや、オーバーコート剤の市販品として、JSR社製「オプトマーSS6699G」)が挙げられる。
本発明の表示装置としては液晶表示装置、プラズマディスプレイ表示装置、EL表示装置、CRT表示装置などの表示装置などを言う。
表示装置の定義や各表示装置の説明は例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。
本発明の表示装置のうち、液晶表示装置は特に好ましい。液晶表示装置については例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。
本発明が適用できる液晶表示装置に特に制限はなく、例えば上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
本発明はこれらのなかで特にカラーTFT方式の液晶表示装置に対して有効である。カラーTFT方式の液晶表示装置については例えば「カラーTFT液晶ディスプレイ(共立出版(株)1996年発行)」に記載されている。
さらに本発明はもちろんIPSなどの横電界駆動方式、MVAなどの画素分割方式などの視野角が拡大された液晶表示装置にも適用できる。これらの方式については例えば「EL、PDP、LCDディスプレイ-技術と市場の最新動向-(東レリサーチセンター調査研究部門 2001年発行)」の43ページに記載されている。
本発明のカラーフィルターはテレビ、パーソナルコンピュータ、液晶プロジェクター、ゲーム機、携帯電話などの携帯端末、デジタルカメラ、カーナビなどの用途に特に制限なく適用できる。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
なお、以下の実施例において、特に断りのない限り「%」および「部」は、「質量%」および「質量部」を表し、分子量とは重量平均分子量のことを示す。
[着色感光性樹脂組成物の調製]
(K顔料分散物1の調製)
下記K顔料分散物1の組成となるようにカーボンブラック、分散剤、ポリマー及び溶剤を混合し、3本ロールとビーズミルを用いてK顔料分散物1を得た。
なお、表1に記載された量は質量基準の部数である。また各成分は詳しくは以下の組成となっている。
・カーボンブラック(デグッサ社製 Nipex35) : 13.1%
・下記分散剤1 : 0.65%
・ポリマー : 6.72%
(ベンジルメタクリレート/メタクリル酸=72/28モル比のランダム共重合物、分子量3.7万)
・プロピレングリコールモノメチルエーテルアセテート : 79.53%
・ポリマー : 27%
(ベンジルメタクリレート/メタクリル酸=78/22モル比のランダム共重合物、分子量3.8万)
・プロピレングリコールモノメチルエーテルアセテート : 73%
・ペンタエリスリトールテトラアクリレート : 75%
(NKエステル A-TMMT、新中村化学工業製)
・メチルエチルケトン : 25%
・2,4-ビス(トリクロロメチル)-6-[4’-(N,N-ビス(エトキシカルボニルメチル)アミノ-3’-ブロモフェニル]-s-トリアジン
: 100%
商品名:メガファック F-780F(大日本インキ製)
・下記構造物1 : 30%
・メチルエチルケトン : 70%
超高圧水銀灯を有するプロキシミティー型露光機(日立ハイテク電子エンジニアリング株式会社製)で、基板とマスク(画像パターンを有す石英露光マスク)を垂直に立てた状態で、露光マスク面と黒色感光層K1の間の距離を200μmに設定し、窒素雰囲気下、黒色感光層K1側から露光量300mJ/cm2でパターン露光した。
また、触針式膜厚計(P-10;Tencor Instrument製)で測定した膜厚d2は2.33μmであった。
以上より、W1/W2=1.14、d1/d2=0.305であった。
上記で得られた離画壁が形成された基板上に、予めフッ素系界面活性剤(住友3M社製、フロラードFC-430)が0.5%(感光性樹脂の固形分に対して)内添してあるアルカリ可溶の感光性樹脂(ヘキストシャパン社製、ポジ型フォトレジストAZP4210)を膜厚2μmとなるようにスリット状ノズルを用いて塗布し、温風循環乾燥機中で90℃、30分間の熱処理を行った。次いで、110mJ/cm2(38mW/cm2×2.9秒)の露光量で離画壁の形成された基板の裏面(離画壁が形成されていない面)から、基板と離画壁を介して露光した。無機アルカリ現像液(ヘキストジャパン社製、AZ400Kデベロッパー、1:4)中に80秒間浸漬揺動した後、純水中で30~60秒間リンス処理を行った。次いで離画壁上に撥水性樹脂層を形成した。これにより画素内外(離画壁に囲まれた凹部と離画壁)に表面エネルギー差を設けた。
撥水性樹脂層形成後の画素内外の表面エネルギーは、画素外(樹脂層上)が10~15dyne/cm、画素内(ガラス基板上、離画壁に囲まれた凹部)は55dyne/cm前後であった。
下記の成分のうち、先ず、下記組成となるように顔料、高分子分散剤及び溶剤を混合し、3本ロールとビーズミルを用いて顔料分散液を得た。その顔料分散液をディソルバー等で十分攪拌しながら、その他の材料を少量ずつ添加し、赤色(R)画素用着色液体組成物(以下、「画素用着色インク組成物」ということがある)を調製した。
〈赤色画素用着色液体組成物の組成〉
・顔料(C.I.ピグメントレッド254) : 5部
・高分子分散剤(AVECIA社製ソルスパース24000) : 1部
・バインダー(グリシジルメタクリレート-スチレン共重合体) : 3部
・第一エポキシ樹脂 : 2部
(ノボラック型エポキシ樹脂、油化シェル社製エピコート154)
・第二エポキシ樹脂 : 5部
(ネオペンチルグリコールジグリシジルエーテル)
・硬化剤(トリメリット酸) : 4部
・溶剤:3-エトキシプロピオン酸エチル : 80部
さらに上記組成中のC.I.ピグメントレッド254に代えてC.I.ピグメントブルー15:6を同量用いるほかは赤色画素用着色インク組成物の場合と同様にして青色(B)画素用着色インク組成物を調製した。
~評価基準~
A : 欠陥数0~2個
B : 欠陥数3~5個
C : 欠陥数6~10個
D : 欠陥数11~25個
E : 欠陥数26個以上
得られた液晶表示装置について、色彩輝度計BM-5A(トプコン社製)を用いてその輝度(Y)を測定し、明るさを下記評価基準に従って評価した。
~評価基準~
A : 875cd/m2以上
B : 850以上875cd/m2未満
C : 825以上850cd/m2未満
D : 800以上825cd/m2未満
E : 800cd/m2未満
[黒色感光性転写材料K1の調製]
厚さ75μmのポリエチレンテレフタレートフィルム仮支持体の上に、スリット状ノズルを用いて、下記処方H1からなる熱可塑性樹脂層用塗布液を塗布、乾燥させた。次に、下記処方P1からなる中間層用塗布液を塗布、乾燥させた。更に、前記黒色組成物K1を塗布、乾燥させた。このようにして仮支持体の上に乾燥膜厚が15.1μmの熱可塑性樹脂層と、乾燥膜厚が1.6μmの中間層と、光学濃度が4.0となるように乾燥膜厚が2.2μmの黒色感光層を設け、最後に保護フイルム(厚さ12μmポリプロピレンフィルム)を圧着した。こうして仮支持体と熱可塑性樹脂層と中間層(酸素遮断膜)とブラック(K)の黒色感光層とが一体となった転写材料を作製し、サンプル名を黒色感光性転写材料K1とした。
・メタノール : 11.1部
・プロピレングリコールモノメチルエーテルアセテート : 6.36部
・メチルエチルケトン : 52.4部
・メチルメタクリレート/2-エチルヘキシルアクリレート/ベンジルメタクリレート/メタクリル酸共重合体(共重合組成比(モル比)=55/11.7/4.5/28.8、分子量=10万、Tg≒70℃) : 5.83部
・スチレン/アクリル酸共重合体(共重合組成比(モル比)=63/37、平均分子量=1万、Tg≒100℃) : 13.6部
・2,2-ビス[4-(メタクリロキシポリエトキシ)フェニル]プロパン(新中村化学工業(株)製) : 9.1部
・フッ素系ポリマー : 0.54部
(C6F13CH2CH2OCOCH=CH2 40部と H(OCH(CH3)CH2)7OCOCH=CH2 55部と H(OCH2CH2)7OCOCH=CH2 5部との共重合体、平均分子量3万、メチルエチルケトン30%溶液、大日本インキ化学工業製、商品名:メガファックF780F)
・PVA205 : 32.2部
(ポリビニルアルコール、(株)クラレ製、鹸化度=88%、重合度550)
・ポリビニルピロリドン : 14.9部
(アイエスピー・ジャパン社製、K-30)
・蒸留水 : 524部
・メタノール : 429部
また、触針式膜厚計(P-10;Tencor Instrument製)で測定した膜厚d2は2.33μmであった。
離画壁を形成した基板に、カソードカップリング方式平行平板型プラズマ処理装置を用いて、以下の条件にてプラズマ撥水化処理を行った。
使用ガス:CF4ガス、流量:80sccm、圧力:40Pa、RFパワー:50W、処理時間:30sec
また、得られた液晶表示装置について、実施例1と同様にして明るさを評価した。
実施例2において黒色組成物K1の代わりに、表1の実施例3~6に記載の組成となるように黒色組成物K3~K6をそれぞれ調製した。これを用いて実施例2と同様にして黒色転写材料K3~K6をそれぞれ作製し、これを用いたこと以外は実施例2と同様にして、基板上に離画壁を形成するとともに、それぞれのW1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例2と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
実施例6において、離画壁作製時の露光量70mJ/cm2の代わりに、露光量を40mJ/cm2、150mJ/cm2とした以外は実施例6と同様にして基板上に離画壁を形成するとともに、それぞれのW1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例6と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
実施例2において黒色組成物K1の代わりに、表1の実施例9~11に記載の組成となるように黒色組成物K9~K11をそれぞれ調製した。これを用いて実施例2と同様にして黒色転写材料K9~K11をそれぞれ作製し、これを用いたこと以外は実施例2と同様にして、基板上に離画壁を形成するとともに、それぞれのW1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例2と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
〈R顔料分散物1の組成〉
・顔料(C.I.ピグメントレッド177) : 18%
・ポリマー : 12%
(ベンジルメタクリレート/メタクリル酸=72/28モル比のランダム共重合物、分子量3.7万)
・プロピレングリコールモノメチルエーテルアセテート : 70%
実施例2の黒色組成物K1の代わりに、表1の比較例1に記載の組成となるように黒色組成物K21を調製した。これを用いて実施例2と同様にして黒色転写材料K21を作製した。
実施例2の離画壁作製時の露光量70mJ/cm2の代わりに、露光量を150mJ/cm2とした以外は実施例2と同様にして基板上に離画壁を形成するとともに、W1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例2と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
比較例1における黒色組成物K21を用い、比較例1の離画壁作製時の露光量150mJ/cm2の代わりに、露光量を400mJ/cm2とした以外は比較例1と同様にして基板上に離画壁を形成するとともに、W1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例2と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
比較例1において黒色組成物K21の代わりに、表1の比較例3、4に記載の組成となるように黒色組成物K23、K24をそれぞれ調製した。これを用いて比較例1と同様にして黒色転写材料K23、K24を作製し、比較例1と同様にして基板上に離画壁を形成するとともに、W1、d1、d2を求めた。
さらに、上記で得られた基板を用いたこと以外は実施例2と同様にしてカラーフィルターを作製し、引き続き液晶表示装置を作製した。
実施例1と同様にして評価したカラーフィルターの画素欠陥、液晶表示装置の明るさの評価結果を表1中に併せて示した。
モノマー液2は、DPHA(ジペンタエリスリトールヘキサアクリレート、日本化薬(株)製)のプロピレングリコールモノメチルエーテルアセテート溶液(76%)である。
重合開始剤2は、Irgacure819(チバ・ジャパン社製)を、重合開始剤3はIrgacure379(チバ・ジャパン社製)を、重合開始剤4はIrgacureOXE01(チバ・ジャパン社製)をそれぞれ表す。
また、添加剤1は、NBCA(10-n-ブチル-2-クロロアクリドン、黒金化成社製)を、添加剤2は、EAB-F(光重合開始助剤、保土谷化学工業(株)製))をそれぞれ意味する。
Claims (11)
- 黒色の色材を含む着色剤と、アルカリ可溶性樹脂と、重合性基を3つ以上有する重合性化合物と、重合開始剤または重合開始系と、溶剤と、を含む着色感光性樹脂組成物であって、
透明基板上に光学濃度が4.0となるように前記着色感光性樹脂組成物を含む感光性樹脂層を形成し、
前記感光性樹脂層の前記透明基板に対向する面とは反対の面側から、マスクを介して前記感光性樹脂層を露光・現像処理して形成される第1のパターンの線幅W1の前記マスクの線幅W2に対する比W1/W2が0.7から1.5の範囲となる露光・現像条件で得られる前記第1のパターンの膜厚d2と、
前記感光性樹脂層の前記透明基板に対向する面側から、マスクと前記透明基板とを介して、前記W1/W2が0.7から1.5の範囲となる露光・現像条件で、前記感光性樹脂層を露光・現像処理して得られる第2のパターンの膜厚d1との比d1/d2が0.3以上である着色感光性樹脂組成物。 - 前記W1/W2が0.8から1.2の範囲となる露光・現像条件における前記d1/d2が0.3から0.7の範囲である請求項1に記載の着色感光性樹脂組成物。
- 前記着色剤は、少なくともカーボンブラックを含有する請求項1または請求項2に記載の着色感光性樹脂組成物。
- 前記重合開始剤または重合開始系は、少なくとも1種のアシルホスフィンオキサイド系開始剤を含有する請求項1~請求項3のいずれか1項に記載の着色感光性樹脂組生物。
- 前記重合性基を3つ以上有する重合性化合物は、3官能のアクリルモノマーおよび4官能のアクリルモノマーの少なくとも1種である請求項1~請求項4のいずれか1項に記載の着色感光性樹脂組生物。
- 請求項1~請求項5のいずれか1項に記載の着色感光性樹脂組成物から形成された感光性樹脂層が仮支持体上に設けられた感光性転写材料。
- 基板と、請求項1~請求項5のいずれか1項に記載の着色感光性樹脂組成物を用いて形成されると共に前記基板上に配置された遮光部と、を備えるカラーフィルター。
- 前記遮光部は、請求項6に記載の感光性転写材料を用いて形成された請求項7に記載のカラーフィルター。
- 前記遮光部の光学濃度が3.5以上である請求項7または請求項8に記載のカラーフィルター。
- 前記遮光部の膜厚が1.5μm以上である請求項7~請求項9のいずれか1項に記載のカラーフィルター。
- 請求項7~請求項10のいずれか1項に記載のカラーフィルターを備える液晶表示装置。
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JP6888148B2 (ja) * | 2020-04-01 | 2021-06-16 | 富士フイルム株式会社 | 転写フィルム、静電容量型入力装置の電極保護膜、積層体および静電容量型入力装置 |
TWI815388B (zh) * | 2022-04-01 | 2023-09-11 | 元太科技工業股份有限公司 | 軟性基板及其製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004219696A (ja) * | 2003-01-15 | 2004-08-05 | Fuji Photo Film Co Ltd | 感光性転写材料、及びカラーフィルタ |
JP2007025243A (ja) * | 2005-07-15 | 2007-02-01 | Asahi Kasei Electronics Co Ltd | ブラックマトリックス基板の製造方法 |
JP2007206370A (ja) * | 2006-02-01 | 2007-08-16 | Toppan Printing Co Ltd | 着色アルカリ現像型感光性樹脂組成物及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタ |
JP2007248678A (ja) * | 2006-03-15 | 2007-09-27 | Toppan Printing Co Ltd | 着色アルカリ現像型感光性樹脂組成物、及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタ |
WO2008084853A1 (ja) * | 2007-01-12 | 2008-07-17 | Toyo Ink Mfg. Co., Ltd. | 着色組成物、カラーフィルタ、及びその製造方法 |
-
2010
- 2010-05-17 KR KR1020127008112A patent/KR20120086693A/ko not_active Application Discontinuation
- 2010-05-17 WO PCT/JP2010/058307 patent/WO2011040083A1/ja active Application Filing
- 2010-05-17 CN CN2010800432880A patent/CN102576190A/zh active Pending
- 2010-05-20 TW TW99116197A patent/TW201111907A/zh unknown
- 2010-06-15 JP JP2010136522A patent/JP2011095716A/ja not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004219696A (ja) * | 2003-01-15 | 2004-08-05 | Fuji Photo Film Co Ltd | 感光性転写材料、及びカラーフィルタ |
JP2007025243A (ja) * | 2005-07-15 | 2007-02-01 | Asahi Kasei Electronics Co Ltd | ブラックマトリックス基板の製造方法 |
JP2007206370A (ja) * | 2006-02-01 | 2007-08-16 | Toppan Printing Co Ltd | 着色アルカリ現像型感光性樹脂組成物及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタ |
JP2007248678A (ja) * | 2006-03-15 | 2007-09-27 | Toppan Printing Co Ltd | 着色アルカリ現像型感光性樹脂組成物、及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタ |
WO2008084853A1 (ja) * | 2007-01-12 | 2008-07-17 | Toyo Ink Mfg. Co., Ltd. | 着色組成物、カラーフィルタ、及びその製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013064993A (ja) * | 2011-08-31 | 2013-04-11 | Fujifilm Corp | カラーフィルタの製造方法、カラーフィルタ、及び固体撮像素子 |
US9632222B2 (en) | 2011-08-31 | 2017-04-25 | Fujifilm Corporation | Method for manufacturing a color filter, color filter and solid-state imaging device |
WO2020105457A1 (ja) * | 2018-11-20 | 2020-05-28 | 富士フイルム株式会社 | 転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法 |
JPWO2020105457A1 (ja) * | 2018-11-20 | 2021-10-14 | 富士フイルム株式会社 | 転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法 |
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TW201111907A (en) | 2011-04-01 |
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