CN101743514A - Color composition and color filter using the same - Google Patents
Color composition and color filter using the same Download PDFInfo
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- CN101743514A CN101743514A CN200880024876A CN200880024876A CN101743514A CN 101743514 A CN101743514 A CN 101743514A CN 200880024876 A CN200880024876 A CN 200880024876A CN 200880024876 A CN200880024876 A CN 200880024876A CN 101743514 A CN101743514 A CN 101743514A
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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
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
Disclosed is a color composition containing a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a coloring agent and an organic solvent. The ratio of the solubility parameter MSP of the polymerizable monomer relative to the double-bond equivalent weight MDC of the polymerizable monomer, namely MSP/MDC is not more than 0.10, and the ratio of the solubility parameter PSP of the transparent resin relative to the double-bond equivalent weight PDC of the transparent resin, namely PSP/PDC is not less than 0.012. The polymerizable monomer is contained in an amount of 30-150% by weight relative to the transparent resin. Also disclosed is a color filter which comprises, on a substrate, a filter segment made of the color composition.
Description
Technical Field
The present invention relates to a coloring composition and a color filter which are suitably used for manufacturing a color filter constituting a color liquid crystal display device, a color image pickup tube element, and the like.
Background
In recent years, liquid crystal display devices have been used for television monitors, personal computer monitors, mobile devices, and the like. In order to improve color reproducibility of color filters used in liquid crystal display devices, the level of requirements for brightness, color purity, and the like is increasing. Further, since liquid crystal display devices have been used for a long time, color filters are also strongly required to have qualities related to resistance, such as heat resistance and light resistance. Further, the level of requirements for the color composition used for producing color filters, such as coating uniformity, sensitivity, developability, and pattern shape, when forming each color filter segment, is increasing. In order to meet these demands, the concentration of a coloring material such as a pigment in the coloring composition is increased, and the component concentrations of the photocurable resin and the monomer are decreased accordingly.
In addition, in order to cope with the continuously increasing demand of the liquid crystal display device, in the manufacture of the color filter, the production time can also be shortened by simplifying the process.
However, increasing the concentration of the coloring material in the coloring composition to reduce the photocurable component or shortening the ultraviolet irradiation time to simplify the manufacturing process of the color filter may result in a colored coating film with poor curing. Here, the colored coating film having poor curing means a colored coating film in which a portion that is sufficiently cured and a portion that is insufficiently cured are mixed in a portion to be cured. When a poorly cured colored coating film is subjected to alkali development, a color difference occurs between a portion that is sufficiently cured and a portion that is insufficiently cured.
The present inventors have attempted to solve the problem of the occurrence of the above-mentioned color difference by the prior art.
First, a method disclosed in japanese patent laid-open No. 2005-099488, that is,: the use of a photosensitive coloring composition containing a photopolymerization initiator with high sensitivity can solve the curing failure of a coating film even with a small amount of a photocurable component and a small amount of ultraviolet irradiation. However, even when the content of the photopolymerization initiator is increased by using a high-sensitivity photopolymerization initiator, the amount of the photocurable component to be cured is limited, and thus the cured coating becomes saturated, and a cured coating film free from color difference due to curing failure is not obtained.
Next, a photosensitive composition disclosed in japanese unexamined patent application publication No. 2002-318453, which contains an a component composed of a polyfunctional (meth) acrylic monomer, a B component composed of a polymer having a structural unit containing a specific cyclic hydrocarbon, a C component composed of a monofunctional monomer, and a D component composed of at least one of a photopolymerization initiator and a photosensitizer in a specific ratio and has alkali resistance, was studied. However, since the component B composed of a polymer contained in the photosensitive composition cannot be cured by ultraviolet irradiation, peeling of the coating film occurs during alkali development, and rather, a large color difference occurs.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a colored composition having high curability due to ultraviolet rays, and a color filter having a filter segment in which color difference due to curing failure is not visible.
According to 1 aspect of the present invention, there is provided a coloring composition comprising a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a coloring material, and an organic solvent, wherein the polymerizable monomer has a solubility parameter MSPDouble bond equivalent M to the polymerizable monomerDCRatio of (A to B)SP/MDCIs 0.10 or less, and the solubility parameter P of the transparent resinSPDouble bond equivalent P to the transparent resinDCRatio P ofSP/PDC0.012 or more, and the content of the polymerizable monomer is 30 to 150% by weight of the transparent resin.
Further, according to another aspect of the present invention, there is provided a color filter having filter segments formed from the colored composition of the present invention on a substrate.
Detailed Description
First, the coloring composition of the present invention will be specifically described.
The coloring composition of the present invention contains a polymerizable monomer having an ethylenically unsaturated double bond (hereinafter referred to as polymerizable monomer), a transparent resin having an ethylenically unsaturated double bond, a coloring material, and an organic solvent.
In the coloring composition of the present invention, the solubility parameter M of the polymerizable monomerSPDouble bond equivalent M to polymerizable monomerDCRatio of (A to B)SP/MDCIs 0.10 or less, and the solubility parameter P of the transparent resinSPDouble bond equivalent P to transparent resinDCRatio P ofSP/PDCIs 0.012 or more, and the polymerizable monomer is present in a proportion of 30 to 150% by weight of the transparent resin.
Solubility parameter M of the polymerizable monomer in the present inventionSPAccording to "ポリマ - エンジニアリング - アンド - サイエンス (Polymer Eng.&Sci.) "volume 14, No. 2 (1974), and P.148 to P.154, i.e., the following formula (1).
Formula (1): mSP＝(∑Δei/∑Δvi)1/2
In the formula (1), Δ eiIs the evaporation energy at 25 ℃ attributed to an atom or group, Δ viIs the molar volume of an atom or group at 25 ℃.
Delta e in the formula (1)iAnd Δ viAre values assigned to i atoms and groups in a molecule. Table 1 shows representative examples of values of Δ e and Δ v given to atoms or groups.
TABLE 1
Note: ph represents a benzene ring
For example, the solubility parameter of 2-hydroxyethyl acrylate represented by the following structural formula (2) is calculated as follows.
Formula (2):
that is to say that the first and second electrodes,since 2-hydroxyethyl acrylate contains 1 ═ CH21-CH ═ 1-COO-, 2-CH2-, 1-OH (C adjacent), thus its ∑ Δ ei1030+1030+4300+1180 × 2+5220 ═ 13940 (cal/mol). In addition, Σ Δ vi28.5+13.5+18+16.1 × 2+13 ═ 105.2 (cm)3Mol). Thus, the solubility parameter M of 2-hydroxyethyl acrylateSPIs (Σ Δ e)i/∑Δvi)1/2＝11.5(cal/cm3)。
In addition, the solubility parameter of a mixture of 2 or more polymerizable monomers is calculated according to the following formula:
MSPmix＝aM1MSPM1+aM2MSPM2+aM3MSPM3+…+aMnMSPMn
wherein,
MSPmixis the solubility parameter of the mixture of polymerizable monomers,
MSPM1as a solubility parameter of the polymerizable monomer 1,
MSPM2as a solubility parameter of the polymerizable monomer 2,
MSPM3as a solubility parameter of the polymerizable monomer 3,
…
MSPMnas the solubility parameter of the polymerizable monomer n,
aM1the weight fraction of the polymerizable monomer 1 in the mixture of polymerizable monomers,
aM2the weight fraction of the polymerizable monomer 2 in the mixture of polymerizable monomers,
aM3the weight fraction of the polymerizable monomer 3 in the mixture of polymerizable monomers,
…
aMnis the weight fraction of the polymerizable monomer n in the mixture of polymerizable monomers.
The double bond equivalent of the polymerizable monomer is calculated from the following formula, and is a measure of the amount of double bonds contained in the molecule of the polymerizable monomer 1. If the compounds have the same molecular weight, the smaller the value of the double bond equivalent, the larger the amount of the double bond.
< equivalent double bond of polymerizable monomer > < molecular weight of polymerizable monomer >/< number of double bonds in molecule of polymerizable monomer 1 >
Further, the double bond equivalent of the polymerizable monomer mixture of 2 or more species is calculated according to the following formula:
MDCmix＝aM1MDCM1+aM2MDCM2+aM3MDCM3+…+aMnMDCMn
wherein,
MDCmixis the double bond equivalent weight of the mixture of polymerizable monomers,
MDCM1the double bond equivalent weight of the polymerizable monomer 1,
MDCM2the double bond equivalent weight of the polymerizable monomer 2,
MDCM3the double bond equivalent weight of the polymerizable monomer 3,
…
MDCMnthe double bond equivalent weight of the polymerizable monomer n,
aM1the weight fraction of the polymerizable monomer 1 in the mixture of polymerizable monomers,
aM2the weight fraction of the polymerizable monomer 2 in the mixture of polymerizable monomers,
aM3the weight fraction of the polymerizable monomer 3 in the mixture of polymerizable monomers,
…
aMnis the weight fraction of the polymerizable monomer n in the mixture of polymerizable monomers.
Solubility parameter M of polymerizable monomerSPDouble bond equivalent M to polymerizable monomerDCRatio of (A to B)SP/MDCIf the amount exceeds 0.1, the surface of the coating film is cured by ultraviolet irradiation, and cracks or the like may occur in the cured coating film. MSP/MDCPreferably 0.03 or more, more preferably 0.05 or more and less than 0.07.
The polymerizable monomer contained in the coloring composition of the present invention preferably has a double bond equivalent of 120 to 350, more preferably 150 to 300. When the double bond equivalent of the polymerizable monomer is less than 120, the surface of the coating film may be cured by ultraviolet irradiation, and cracks may be formed in the cured coating film. When the double bond equivalent of the polymerizable monomer is more than 350, the sensitivity of the coloring composition is insufficient, and the coating film may not be cured even by irradiation with ultraviolet rays.
Examples of the polymerizable monomer include 2-hydroxyethyl acrylate (solubility parameter (SP): 11.5, double bond equivalent (DC): 116), 2-hydroxyethyl methacrylate (SP: 13.2, DC: 130), 2-hydroxypropyl acrylate (SP: 11.7, DC: 130), 2-hydroxypropyl methacrylate (SP: 10.7, DC: 143), cyclohexyl methacrylate (SP: 9.3, DC: 154), cyclohexyl methacrylate (SP: 9.2, DC: 168), polyethylene glycol diacrylate (SP: 9.9, DC: 151), polyethylene glycol dimethacrylate (SP: 9.8, DC: 165), pentaerythritol triacrylate (SP: 12.2, DC: 99), pentaerythritol trimethacrylate (SP: 11.6, DC: 113), trimethylolpropane triacrylate (SP: 9.9, DC: 100), Trimethylolpropane trimethacrylate (SP: 11.4, DC: 113), dipentaerythritol hexaacrylate (SP: 10.8, DC: 97), dipentaerythritol hexamethacrylate (SP: 10.4, DC: 111), tricyclodecyl acrylate (SP: 11.6, DC: 84), tricyclodecyl methacrylate (SP: 11.0, DC: 98), melamine acrylate (SP: 11.3, DC: 149), melamine methacrylate (SP: 10.9, DC: 163), epoxy acrylate (SP: 8.7, DC: 295), epoxy methacrylate (SP: 8.6, DC: 309), and various acrylates and methacrylates, acrylic acid (SP: 11.1, DC: 72), methacrylic acid (SP: 10.7, DC: 86), styrene (SP: 7.9, DC: 104), vinyl acetate (SP: 8.9, DC: 86), methacrylamide (SP: 14.2, DC: 71, 71), Methacrylamide (SP: 13.3, DC: 85), N-methylolacrylamide (SP: 15.4, DC: 101), N-methylolmethacrylamide (SP: 14.5, DC: 115), acrylonitrile (SP: 11.1, DC: 53), and the like. It is also possible to use a polymerizable monomer in which a part of the carbon chain is modified with caprolactone, ethylene oxide, or propylene oxide.
The polymerizable monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The transparent resin having an ethylenically unsaturated double bond (hereinafter referred to as a photocurable transparent resin) in the present invention has an ethylenically unsaturated double bond and preferably has a transmittance of 80% or more, more preferably 95% or more, in a total wavelength region of 400 to 700nm in a visible light region. The solubility parameter of the photocurable transparent resin is calculated from the formula of Fedors in the same manner as the polymerizable monomer. However, in the case of the photocurable transparent resin, the calculation is made based on the theoretical monomer composition (molar ratio) constituting the resin, which is shown by the following formula.
Solubility parameter P of the Photocurable transparent resinSP＝Wta×SPa+Wtb×SPb+Wtc×SPc…
Wherein,
and (Wta): the mole fraction of the monomer A is,
wtb: the mole fraction of the monomer B is,
wtc: the mole fraction of the monomer C is,
…
and (4) SPa: the solubility parameter of the monomer a is,
SPb: the solubility parameter of the monomer B is,
SPc: the solubility parameter of the monomer B is,
…
for example, when the constituent monomers of the photocurable transparent resin are 70% by weight of methacrylic acid (molecular weight: 86, solubility parameter: 10.7) and 30% by weight of methyl methacrylate (molecular weight: 100, solubility parameter: 9.3), the solubility parameter of the resin is (mole fraction of methacrylic acid) × (solubility parameter of methacrylic acid) + (mole fraction of methyl methacrylate) × (solubility parameter of methyl methacrylate) ═ 70/86)/(70/86+30/100) × 10.7+ (30/100)/(70/86+30/100) × 9.3 ═ 10.32.
Further, the solubility parameter of the mixture of 2 or more photocurable transparent resins is calculated according to the following formula:
PSPmix＝aP1MSPM1+aP2MSPM2+aP3MSPM3+…+aPnMSPMn
wherein,
PSPmixis a solubility parameter of a mixture of photocurable transparent resins,
PSPS1as the solubility parameter of the photocurable transparent resin 1,
PSPS2as the solubility parameter of the photocurable transparent resin 2,
PSPS3as the solubility parameter of the photocurable transparent resin 3,
…
MSPSnas a solubility parameter of the photocurable transparent resin n,
aP1is the weight fraction of the photocurable transparent resin 1 in the mixture of photocurable transparent resins,
aP2is a light-curable transparent treeThe weight fraction of the photocurable transparent resin 2 in the mixture of fats,
aP3is the weight fraction of the photocurable transparent resin 3 in the mixture of photocurable transparent resins,
…
aPnis the weight fraction of the photocurable transparent resin n in the mixture of photocurable transparent resins.
The double bond equivalent of the photocurable transparent resin is calculated from the following formula, which is a measure of the amount of double bonds contained in 1 molecule of the photocurable transparent resin. In the case of the photocurable transparent resin having the same molecular weight, the smaller the numerical value of the double bond equivalent, the larger the amount of the double bonds.
< double bond equivalent weight of Photocurable transparent resin > < weight average molecular weight of Photocurable transparent resin >/< number of double bonds in 1 molecule of Photocurable transparent resin >
The double bond equivalent of the mixture of 2 or more photocurable transparent resins is calculated according to the following formula:
PDCmix＝aP1PDCP1+aP2PDCP2+aP3PDCP3+…+aPnPDCPn
wherein,
PDCmixis the double bond equivalent of the mixture of the photocurable transparent resins,
PDCP1the double bond equivalent of the photocurable transparent resin 1,
PDCP2the double bond equivalent of the photocurable transparent resin 2,
PDCP3the double bond equivalent of the photocurable transparent resin 3,
…
PDCPnthe double bond equivalent of the photocurable transparent resin n,
aP1is the weight fraction of the photocurable transparent resin 1 in the mixture of photocurable transparent resins,
aP2is the weight fraction of the photocurable transparent resin 2 in the mixture of photocurable transparent resins,
aP3is the weight fraction of the photocurable transparent resin 3 in the mixture of photocurable transparent resins,
…
aPnis the weight fraction of the photocurable transparent resin n in the mixture of photocurable transparent resins.
Solubility parameter P of the Photocurable transparent resinSPDouble bond equivalent P to the photocurable transparent resinDCRatio P ofSP/PDCWhen the content is 0.012 or less, the photocurability of the colored composition is lowered, and the coating film is not sufficiently cured even by irradiation with ultraviolet rays. PSP/PDCPreferably 0.05 or less, more preferably 0.015 or more and 0.045 or less.
The photocurable transparent resin contained in the colored composition of the invention preferably has a double bond equivalent of 200 to 800, more preferably 300 to 700. When the double bond equivalent of the photocurable transparent resin is less than 200, the surface of the coating film may be cured by ultraviolet irradiation, and cracks may be formed in the cured coating film. When the double bond equivalent of the photocurable transparent resin is more than 800, sufficient sensitivity of the colored composition cannot be obtained, and the coating film cannot be sufficiently cured even by irradiation with ultraviolet rays.
As the photocurable transparent resin, a resin obtained by reacting a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group with a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer can be used. Further, a linear polymer containing an acid anhydride, such as a styrene-maleic anhydride copolymer or an α -olefin-maleic anhydride copolymer, can be half-esterified with a (meth) acrylic compound having a hydroxyl group, such as hydroxyalkyl (meth) acrylate.
The photocurable transparent resin may be used alone in 1 kind, or in a mixture of 2 or more kinds.
In the colored composition of the present invention, the content of the polymerizable monomer is 30 to 150% by weight, and preferably 50 to 100% by weight, based on the photocurable transparent resin. In the colored composition of the present invention, the polymerizable monomer functions as a curing agent, and the photocurable transparent resin functions as a curing aid. The photocurable transparent resin itself has less influence on photocuring than the polymerizable monomer, and the amount of the polymerizable monomer is determined as described above since the polymerizable monomer itself is cured by light. The photocurable transparent resin and the polymerizable monomer are preferably contained in a well-balanced manner.
When a coating film formed using the coloring composition of the present invention is irradiated with ultraviolet rays, polymerization of the polymerizable monomer is promoted from the ethylenically unsaturated double bond of the photocurable transparent resin, and the coating film on the portion irradiated with ultraviolet rays is sufficiently cured without causing any curing failure in the whole. When the amount of the polymerizable monomer exceeds 150% by weight of the photocurable transparent resin, the photocurable transparent resin as the starting point of polymerization of the polymerizable monomer is small, and the polymerizable monomer is not sufficiently cured, which is not preferable. When the amount of the polymerizable monomer is less than 30%, the polymerizable monomer is sufficiently cured, but the absolute amount of the polymerizable monomer is decreased, and the curing of the coating film becomes insufficient, which is not preferable.
The photocurable transparent resin may be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, based on 100 parts by weight of the colorant.
The coloring material contained in the coloring composition of the present invention may be an organic pigment or an inorganic pigment alone or a mixture of 2 or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high thermal decomposition resistance are preferable, and organic pigments are generally used.
Specific examples of organic pigments that can be preferably used in the coloring composition of the present invention are shown below by the color index (c.i.).
As the red coloring composition for forming the red filter segment, for example, a red pigment such as c.i. pigment red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272 can be used. A yellow pigment or an orange pigment may be used in combination in the red-colored composition.
As the yellow coloring composition for forming the yellow filter segment, for example, c.i. pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 182, 187, 177, 185, 188, 194, 199, etc. can be used.
As the orange coloring composition for forming the orange filter segment, for example, orange pigments such as c.i. pigment orange 36, 43, 51, 55, 59, 61 can be used.
As the green coloring composition for forming the green filter segment, for example, green pigments such as c.i. pigment green 7, 10, 36, 37 can be used. A yellow pigment may be used in combination in the green-colored composition.
As the blue coloring composition for forming the blue filter segment, for example, blue pigments such as c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, and the like can be used. A violet pigment such as c.i. pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 may be used in combination in the blue-colored composition.
As the cyan coloring composition for forming the cyan filter segment, for example, blue pigments such as c.i. pigment blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81, and the like can be used.
As the magenta coloring composition for forming the magenta filter segment, for example, violet pigments such as c.i. pigment violet 1, 19, c.i. pigment red 144, 146, 177, 169, 81 and red pigments can be used. A yellow pigment may be used in combination in the magenta coloring composition.
Examples of the inorganic pigment include metal oxide powders such as barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, red iron oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide, and ferroferric oxide, metal sulfide powders, and metal powders. In order to ensure good coatability, sensitivity, developability, and the like while achieving a balance between chroma and brightness, an inorganic pigment may be used in combination with an organic pigment.
The coloring composition of the present invention may contain a dye in a range not to lower heat resistance for toning.
Examples of the organic solvent contained in the colored composition of the present invention include 2-heptanone, 4-heptanone, cyclohexanone, N-butyl acetate, isobutyl acetate, isoamyl acetate, N-pentyl acetate, methyl isobutyl ketone, N-butanol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, N-dimethylformamide, 1, 2, 3-trichloropropane, o-chlorotoluene, o-xylene, m-xylene, 3-methoxy-3-methyl-1-butanol, 1, 3-butanediol, and the like, 3-methyl-1, 3-butanediol, 2-methyl-1, 3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, gamma-butyrolactone, N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, N-butyl acetate, O-diethylbenzene, m-diethylbenzene, p-diethylbenzene, o-dichlorobenzene, m-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, methylcyclohexanol, and the like. They may be used alone or in combination of 2 or more. The organic solvent may be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, relative to 100 parts by weight of the colorant in the coloring composition.
A photopolymerization initiator may be added to the colored composition of the present invention.
As the photopolymerization initiator, acetophenone type photopolymerization initiators such as 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin dimethyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acryloylbenzophenone, 4-benzoyl-4' -methyldiphenylsulfide and the like; thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone; 2, 4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphthalen-1-yl) -4, triazine-based photopolymerization initiators such as 6-bis (trichloromethyl) -s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine and 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine; borate-type photopolymerization initiators, carbazole-type photopolymerization initiators, imidazole-type photopolymerization initiators, and the like. The photopolymerization initiator may be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the coloring material in the coloring composition.
The photopolymerization initiator may be used alone or in combination of 2 or more, and as the sensitizer, a compound such as α -acyloxime ester (α -acyloxime ester), acylphosphine oxide, methylphenylglyoxylate, benzil, 9, 10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4, 4 '-diethylisophthalophenone, 3', 4, 4 '-tetrakis (t-butylperoxycarbonyl) benzophenone, 4, 4' -diethylaminobenzophenone, or the like may be used in combination. The sensitizer may be used in an amount of 0.1 to 60 parts by weight relative to 100 parts by weight of the photopolymerization initiator in the coloring composition.
The colored composition of the present invention can be produced by finely dispersing 1 or 2 or more kinds of coloring materials together with the polymerizable monomer and the photopolymerization initiator in the photocurable transparent resin and the organic solvent using various dispersing apparatuses such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. Further, the colored composition containing 2 or more coloring materials can be produced by mixing a mixture of the above-mentioned photocurable transparent resin and an organic solvent in which each coloring material is finely dispersed. When the pigment is dispersed as a coloring material in the above-mentioned photocurable transparent resin and organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, a pigment derivative, or the like may be appropriately contained. The dispersion aid is excellent in dispersion of the pigment and has a large effect of preventing reagglomeration of the pigment after dispersion, and therefore, when a colored composition obtained by dispersing the pigment in the photocurable transparent resin and the organic solvent using the dispersion aid is used, a color filter having excellent transparency can be obtained.
The resin type pigment dispersant includes a pigment affinity site having a property of being adsorbed to a pigment and a site having compatibility with a pigment carrier, and functions to stably disperse the pigment in the pigment carrier by adsorbing the pigment. Specific examples of the resin type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, an oily dispersant such as an amide or a salt thereof formed by the reaction of poly (lower alkylene imine) with a polyester having a free carboxyl group, a water-soluble resin or a water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, a polyester, a modified polyacrylate, an ethylene oxide/propylene oxide adduct, a phosphate, and the like, and these may be used alone or in a mixture of 2 or more.
Examples of the surfactant include anionic surfactants such as polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium lauryl sulfate, monoethanolamine salts of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline may be used alone or in combination of 2 or more.
The pigment derivative is a compound obtained by introducing a substituent into an organic pigment, and generally includes a pale yellow aromatic polycyclic compound such as naphthalene and anthraquinone which are not called pigments. As the pigment derivative, compounds described in Japanese patent application laid-open No. Sho 63-305173, Japanese patent application laid-open No. Sho 57-15620, Japanese patent application laid-open No. Sho 59-40172, Japanese patent application laid-open No. Sho 63-17102, Japanese patent application laid-open No. Hei 5-9469 and the like can be used, and they may be used alone or in combination of 2 or more.
The dispersing aid may be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the colorant.
The colored composition of the present invention may contain a non-photosensitive transparent resin to control solubility or resistance to a developer. The non-photosensitive transparent resin is a transparent resin which has no ethylenically unsaturated double bond and has a transmittance of preferably 80% or more, more preferably 95% or more, in the total wavelength region of 400 to 700nm in the visible light region. Such a non-photosensitive transparent resin includes a thermoplastic resin and a thermosetting resin, and these may be used alone or in a mixture of 2 or more.
Examples of the non-photosensitive thermoplastic resin include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadienes, polyimide resins, and the like. Examples of the non-photosensitive thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
The non-photosensitive thermoplastic resin may be used in an amount of 10 to 1000 parts by weight, preferably 50 to 800 parts by weight, based on 100 parts by weight of the colorant.
In addition, the coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition with time. Examples of the storage stabilizer include hydroquinone compounds such as hydroquinone, methylhydroquinone, 2, 5-di-t-butylhydroquinone, t-butyl- β -benzoquinone, t-butylhydroquinone, and 2, 5-diphenyl-p-benzoquinone, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid, methyl ethers thereof, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphate compounds such as triphenyl phosphate and trinonyl phenyl phosphate, and tert-butyl catechol. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the colorant in the coloring composition.
In addition, an adhesion improver such as a silane coupling agent may be contained to improve adhesion to the substrate.
Examples of the silane coupling agent include vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acryl silanes such as γ -methacryloxypropyltrimethoxysilane, epoxysilanes such as β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) methyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane, β - (3, 4-epoxycyclohexyl) methyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -glycidoxypropyltriethoxysilane, N- β (aminoethyl) γ -aminopropyltrimethoxysilane, N- β -aminoethyltrimethoxysilane, N- β -ethylenepropyltrimethoxysilane, N-ethylenebutyltrimethoxysilane, N-butyltrimethoxysilane, N-butyl, Aminosilanes such as N-beta (aminoethyl) gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane and N-phenyl-gamma-aminopropyltriethoxysilane, and thiosilanes such as gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane. The silane coupling agent may be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the color filter coloring composition.
The colored composition of the present invention is preferably prepared by removing coarse particles having a particle size of 5 μm or more, preferably coarse particles having a particle size of 1 μm or more, more preferably coarse particles having a particle size of 0.5 μm or more, and dust mixed therein, by using a device such as centrifugal separation, sintered filter, or membrane filter.
In order to obtain a uniform coating film without causing coating unevenness, the viscosity of the colored composition of the present invention is preferably adjusted to 10 mPas or less, more preferably 1 to 8 mPas at 25 ℃ by using an E-type viscometer at a rotation speed of 20 rpm.
The coloring composition of the present invention can be prepared in the form of a solvent-developable or alkali-developable coloring resist material.
Next, a color filter having a filter segment formed of the colored composition of the present invention will be described.
The color filter is formed by forming filter segments of at least 2 colors selected from R (red), G (green), B (blue), Y (yellow), M (magenta) and C (cyan) on a transparent or reflective substrate. Each color filter segment can be formed by photolithography using the colored composition of the present invention.
As the transparent substrate, a glass plate, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used.
As the reflective substrate, silicon, a substrate in which a thin film of aluminum, silver/copper/palladium alloy, or the like is formed on the transparent substrate, or the like can be used.
The color filter segment is formed by photolithography, and a color composition prepared as the above-mentioned solvent-developable or alkali-developable color resist is applied to a substrate so that the dry film thickness is 0.2 to 5 μm by a coating method such as spray coating, spin coating, slit coating, or roll coating. The dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in a state of being in contact with or not in contact with the film, as necessary. Thereafter, the resultant is immersed in a solvent or an alkali developing solution, or the developing solution is sprayed by spraying or the like to remove uncured portions and form a desired pattern, and then the same operation is repeated for other colors, whereby a color filter can be produced. Further, heating may be performed as necessary to promote polymerization of the colored resist. By the photolithography method, a color filter with higher accuracy than that by the printing method can be obtained.
As the developing method, a spray developing method, a dip (immersion) developing method, a dip (liquid) developing method, or the like can be used.
In addition, in order to improve the sensitivity of ultraviolet exposure, after the colored resist material is coated and dried, a film for preventing polymerization inhibition by oxygen may be formed by coating and drying a water-soluble or alkali-soluble resin, for example, polyvinyl alcohol or a water-soluble acrylic resin, and then ultraviolet exposure may be performed.
The present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention. In addition, "parts" in the examples means "parts by weight".
Synthesis example 1
560 parts of cyclohexanone was charged into a reaction vessel, the vessel was heated to 80 ℃ while injecting nitrogen gas, and a mixture of 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 45.0 parts of n-butyl methacrylate, 47.0 parts of glycerol monomethacrylate and 4.0 parts of 2, 2' -azobisisobutyronitrile was added dropwise over 1 hour at the same temperature to carry out polymerization.
After the completion of the dropwise addition, the reaction mixture was reacted at 80 ℃ for 3 hours, and then a solution prepared by dissolving azobisisobutyronitrile in 55 parts of cyclohexanone in 1.0 part was added, and the reaction was continued at 80 ℃ for 1 hour to obtain a copolymer solution.
Subsequently, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 120.0 parts of cyclohexanone was added dropwise at 70 ℃ over 3 hours, based on 338 parts of the obtained copolymer solution.
After cooling to room temperature, about 2g of the obtained photocurable transparent resin solution was sampled, heated and dried at 180 ℃ for 20 minutes, and the nonvolatile content was measured, and based on the measurement value, cyclohexanone was added to the synthesized photocurable transparent resin solution so that the nonvolatile content became 20 wt%, thereby preparing a photocurable transparent resin solution a. The weight average molecular weight of the obtained photocurable transparent resin was 20000, the double bond equivalent was 470, and the solubility parameter was 11.0.
Synthesis example 2
A reaction vessel was charged with 520 parts of cyclohexanone, the vessel was heated to 80 ℃ while injecting nitrogen, and a mixture of 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 63.0 parts of 2-hydroxyethyl methacrylate, 66.0 parts of glycerol monomethacrylate and 4.0 parts of 2, 2' -azobisisobutyronitrile was added dropwise at the same temperature over 1 hour to carry out polymerization.
After the completion of the dropwise addition, the reaction was further carried out at 80 ℃ for 3 hours, and then a solution prepared by dissolving azobisisobutyronitrile in 70 parts of cyclohexanone was added thereto, and the reaction was further continued at 80 ℃ for 1 hour to obtain a copolymer solution.
Subsequently, a mixture of 56.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 220.0 parts of cyclohexanone was added dropwise at 70 ℃ over 3 hours, relative to 220 parts of the obtained copolymer solution.
After cooling to room temperature, cyclohexanone was added so that the nonvolatile components became 20% by weight in the same manner as in synthesis example 1, to prepare a photocurable transparent resin solution B. The weight average molecular weight of the obtained photocurable transparent resin was 20000, the double bond equivalent was 270, and the solubility parameter was 11.0.
Synthesis example 3
480 parts of cyclohexanone was charged into a reaction vessel, and the vessel was heated to 80 ℃ while injecting nitrogen gas, and a mixture of 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate, 48.0 parts of benzyl methacrylate, 15.0 parts of glycerol monomethacrylate and 4.0 parts of 2, 2' -azobisisobutyronitrile was added dropwise over 1 hour at the same temperature to carry out polymerization.
After the completion of the dropwise addition, the reaction was further carried out at 80 ℃ for 3 hours, and then a solution prepared by dissolving azobisisobutyronitrile in 80 parts of cyclohexanone in 1.0 part was added, and the reaction was further continued at 80 ℃ for 1 hour to obtain a copolymer solution.
Subsequently, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 55.0 parts of cyclohexanone was added dropwise at 70 ℃ over 3 hours, relative to 445 parts of the obtained copolymer solution.
After cooling to room temperature, cyclohexanone was added so that the nonvolatile components became 20% by weight in the same manner as in synthesis example 1, to prepare a photocurable transparent resin solution C. The weight average molecular weight of the obtained photocurable transparent resin was 20000, the double bond equivalent was 1000, and the solubility parameter was 10.8.
Example 1
After uniformly stirring and mixing a mixture having the following composition, glass beads having a diameter of 1mm were used, and the mixture was dispersed for 5 hours by a sand mill and then filtered through a 5 μm filter to prepare a copper phthalocyanine dispersion.
Composition of the mixture (copper phthalocyanine dispersion):
12.00 parts of epsilon-type copper phthalocyanine pigment (C.I. pigment blue 15:6)
(Heliogen Blue L-6700F manufactured by BASF)
2.40 parts of a dispersant (Solsperse 20000, manufactured by Lubrizol Co., Ltd., Japan)
28.10 parts of Photocurable transparent resin solution A obtained in Synthesis example 1
57.50 parts of cyclohexanone
Subsequently, a mixture having the following composition was stirred and mixed until uniform, and then filtered through a 1 μm filter to obtain a colored composition prepared as a blue resist material. The compositions of the coloring compositions (weight ratio based on the total amount of the coloring compositions as 100) are shown in table 2.
Composition of the mixture (coloring composition):
45.05 parts of copper phthalocyanine dispersion
18.05 parts of Photocurable transparent resin solution A obtained in Synthesis example 1
4.80 parts of caprolactone modified trimethylolpropane triacrylate
Photopolymerization initiator 2.50 parts
(IRGACURE 907, product of Ciba Specialty Chemicals)
0.20 part of a sensitizer (EAB-F, manufactured by Baotu chemical Co., Ltd.)
0.01 part of flatting agent
(BYK-Chemie Japan K.K. "BYK-323")
Cyclohexanone 29.40 parts
Examples 2 to 9 and comparative examples 1 to 7
Pigment dispersions of respective colors were obtained in the same manner as in example 1, except that the compositions of the pigment, the dispersant, the photocurable transparent resin solution and the solvent were changed to the ratios shown in table 2 (the weight ratio of the total amount of the pigment dispersions being 100).
Then, a colored composition prepared as a resist material for each color was obtained in the same manner as in example 1, except that the compositions of the pigment dispersion, the photocurable transparent resin solution, the polymerizable monomer, the photopolymerization initiator, the sensitizer, the organic solvent and the leveling agent were changed to the proportions shown in tables 3-1 and 3-2 (the weight ratio of the total amount of the colored composition to 100).
TABLE 2
| Blue 1 | Blue 2 | Blue color 3 | Red 1 | Red 2 | Green 1 | Green 2 | |
| PB15:6 | 12.00 | 12.00 | 12.00 | ||||
| PR254 | 11.29 | 11.29 | |||||
| PR177 | 1.82 | 1.82 | |||||
| PY199 | 0.44 | 0.44 | |||||
| PG36 | 7.22 | 7.22 | |||||
| PY150 | 5.22 | 5.22 | |||||
| Dispersing agent | 2.40 | 2.40 | 2.40 | 2.40 | 2.40 | 2.40 | 2.40 |
| Resin A | 28.10 | 20.20 | 25.80 | ||||
| Resin B | 28.10 | ||||||
| Resin C | 28.10 | 20.20 | 25.80 | ||||
| Cyclohexanone | 57.50 | 57.50 | 57.50 | 63.84 | 63.84 | 59.36 | 59.36 |
| Total up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
In the context of Table 2, the following examples are,
PB15:6 ═ e type copper phthalocyanine pigment (c.i. pigment blue 15:6) (heiogen blue l-6700F, manufactured by BASF);
PR254 ═ diketopyrrolopyrrole pigment (c.i. pigment Red 254) (product of Ciba specialty chemicals "Irgaphor Red B-CF");
PR177 anthraquinone pigment (c.i. pigment Red 177) (Cromophtal Red A2B, product of Ciba Specialty Chemicals);
PY199 ═ anthraquinone pigment (c.i. pigment Yellow 199) (Cromophtal Yellow GT-AD, product of Ciba Specialty Chemicals);
PG36 ═ copper halide phthalocyanine pigment (c.i. pigment green 36) (lipol green 6YK manufactured by toyoyo ink manufacturers);
PY150 (C.I. pigment yellow 150) (Fanchon fast yellow Y-5688, manufactured by Lanxess Co., Ltd.)
Dispersant "Solsperse 20000" manufactured by Lubrizol corporation of Japan;
resin a is the photocurable transparent resin solution a obtained in synthesis example 1;
resin B is the photocurable transparent resin solution B obtained in synthesis example 2;
resin C is the photocurable transparent resin solution C obtained in synthesis example 3.
In tables 3-1 and 3-2,
a caprolactone-modified trimethylolpropane triacrylate (DAICEL-CYTEC, "Ebecryl 2047", solubility parameter: 10.6, double bond equivalent: 201);
monomer B ═ ethylene oxide modified trimethylolpropane triacrylate
(ARONIX M-350, manufactured by Toyo Synthesis Co., Ltd.; solubility parameter: 10.1, double bond equivalent: 143);
trimethylolpropane triacrylate (NK ester A-TMPT, product of Xinzhongcun chemical Co., Ltd. "solubility parameter: 10.5, double bond equivalent: 99);
resin a is the photocurable transparent resin solution a obtained in synthesis example 1;
resin B is the photocurable transparent resin solution B obtained in synthesis example 2;
resin C is the photocurable transparent resin solution C obtained in synthesis example 3;
a photopolymerization initiator "IRGACURE 907" manufactured by Ciba Specialty Chemicals;
the sensitizer is "EAB-F" from Bao Tugu chemical Co., Ltd;
the leveling agent is BYK-323 manufactured by BYK-Chemie Japan.
The resist materials of the respective colors obtained in examples 1 to 9 and comparative examples 1 to 7 were applied to a glass substrate having a thickness of 100mm × 100mm and 0.7mm by using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after prebaking at 70 ℃ for 20 minutes, 100mJ/cm was performed2Exposure to ultraviolet light. The spectral transmittance of the obtained photocurable film was measured using a microspectrophotometer ("OSP-SP 100" manufactured by olympus optics corporation), and the resultant film was immersed in a 0.25% aqueous solution of sodium hydroxide. After 2 minutes of immersion, the spectral transmittance was measured again using a microspectrophotometer, and the color difference Δ Eab was calculated. Further, after immersing in a 0.25% aqueous sodium hydroxide solution for 2 minutes, observation of development spots was carried out using an optical microscope, and evaluations were carried out on a 4-scale (excellent: no development spots observed, o: small and light development spots observed, Δ: light development spots observed as a whole, and x: dark development spots observed as a whole). The results are shown in Table 4.
TABLE 4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Colour(s) | Blue (B) | Blue (B) | Blue (B) | Blue (B) | Red wine | Green | Blue (B) | Blue (B) |
| Color difference Δ Eab | 0.69 | 1.10 | 1.21 | 2.58 | 0.68 | 0.91 | 2.55 | 2.66 |
| Development of spots | ◎ | ○ | ○ | ○ | ◎ | ◎ | ○ | ○ |
| Example 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Colour(s) | Blue (B) | Blue (B) | Blue (B) | Blue (B) | Blue (B) | Blue (B) | Red wine | Green |
| Color difference Δ Eab | 0.65 | 7.14 | 8.12 | 9.01 | 5.57 | 8.11 | 10.25 | 11.41 |
| Development of spots | ◎ | △ | × | × | △ | × | × | × |
The cured coatings formed using the coloring compositions obtained in examples 1 to 6 had a smaller color difference Δ Eab before and after immersion in an aqueous sodium hydroxide solution than the cured coatings formed using the coloring compositions obtained in comparative examples 1 to 7, and no development mottle was observed, and the results were good.
Further, in the cured coating films obtained using the coloring compositions obtained in examples 7 to 9, the color difference Δ Eab was larger than that in the most preferable example 9 at a blending amount close to the preferable range, and the development mottle was observed to be slightly larger than that in example 9.
As described above, since the coloring composition of the present invention is sufficiently cured by ultraviolet irradiation, a cured coating film formed using the coloring composition of the present invention exhibits sufficient resistance to an alkali developing solution. As a result, the in-plane chromatic aberration of the filter segments included in the color filter disappears, and a favorable liquid crystal display device can be obtained. A good liquid crystal display device can be stably obtained, and the following excellent effects can be produced: the market of liquid crystal display devices, which has been growing rapidly and is being satisfied with a reduction in the fraction defective in the manufacturing line and a reduction in the cost and an increase in the amount of production, is on the rise.
Claims (4)
1. A coloring composition characterized by comprising a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a coloring material and an organic solvent; solubility parameter M of the polymerizable monomerSPDouble bond equivalent M to the polymerizable monomerDCRatio of (A to B)SP/MDCIs 0.10 or less, and the solubility parameter P of the transparent resinSPDouble bond equivalent P to the transparent resinDCRatio P ofSP/PDCIs 0.012 or more, and the content of the polymerizable monomer is the above30-150% of the weight of the bright resin.
2. The coloring composition according to claim 1, wherein the polymerizable monomer has a double bond equivalent MDCIs 120 to 350.
3. Coloring composition according to claim 1 or 2, characterized in that the transparent resin has a double bond equivalent PDCIs 200 to 800.
4. A color filter comprising a filter segment formed from the colored composition according to any one of claims 1 to 3 on a substrate.
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| JP2007189736A JP5075510B2 (en) | 2007-07-20 | 2007-07-20 | Coloring composition and color filter using the same |
| PCT/JP2008/062836 WO2009014044A1 (en) | 2007-07-20 | 2008-07-16 | Color composition and color filter using the same |
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| CN104423149A (en) * | 2013-09-06 | 2015-03-18 | 三星Sdi株式会社 | Photosensitive Resin Composition and Color Filter Using the Same |
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|---|---|---|---|---|
| JP5266958B2 (en) * | 2008-08-22 | 2013-08-21 | 凸版印刷株式会社 | Color filter for liquid crystal display |
| TW201031713A (en) * | 2009-02-13 | 2010-09-01 | Toyo Ink Mfg Co | The coloring composition for color filters and color filters |
| JP5663878B2 (en) * | 2009-02-18 | 2015-02-04 | Jsr株式会社 | Colored radiation-sensitive composition, color filter, and color liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002107930A (en) * | 2000-09-28 | 2002-04-10 | Toppan Printing Co Ltd | Photosensitive resin composition |
| JP4195329B2 (en) * | 2003-03-24 | 2008-12-10 | 大日本印刷株式会社 | Pigment dispersion for coloring resist, photosensitive coloring composition, and color filter |
| JP4597692B2 (en) * | 2005-02-07 | 2010-12-15 | 東洋インキ製造株式会社 | Coloring composition for color filter and color filter |
| JP4597693B2 (en) * | 2004-12-24 | 2010-12-15 | 東洋インキ製造株式会社 | Blue coloring composition for color filter and color filter |
| CN100543585C (en) * | 2004-12-24 | 2009-09-23 | 东洋油墨制造株式会社 | Color composition for color filter and color filter |
| JP5246994B2 (en) * | 2005-08-01 | 2013-07-24 | 東洋インキＳｃホールディングス株式会社 | Photosensitive composition and color filter |
-
2007
- 2007-07-20 JP JP2007189736A patent/JP5075510B2/en active Active
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2008
- 2008-07-16 KR KR1020097026043A patent/KR101431502B1/en active Active
- 2008-07-16 WO PCT/JP2008/062836 patent/WO2009014044A1/en active Application Filing
- 2008-07-16 CN CN2008800248762A patent/CN101743514B/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104423149A (en) * | 2013-09-06 | 2015-03-18 | 三星Sdi株式会社 | Photosensitive Resin Composition and Color Filter Using the Same |
| CN104423149B (en) * | 2013-09-06 | 2019-10-15 | 三星Sdi株式会社 | Photosensitive resin composition and color filter using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5075510B2 (en) | 2012-11-21 |
| TW200912396A (en) | 2009-03-16 |
| JP2009025634A (en) | 2009-02-05 |
| CN101743514B (en) | 2013-09-11 |
| WO2009014044A1 (en) | 2009-01-29 |
| TWI432797B (en) | 2014-04-01 |
| KR101431502B1 (en) | 2014-08-20 |
| KR20100039279A (en) | 2010-04-15 |
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