TWI432797B - Colored composition and color filter using the same - Google Patents

Description

Coloring composition and color filter using the same

The present invention relates to a coloring composition and a color filter which are applied to the manufacture of a color filter constituting a color liquid crystal display device, a color image sensor element, or the like.

In recent years, liquid crystal display devices have been used for television monitor applications, personal computer monitor applications, mobile device applications, and the like. In order to improve the color reproducibility of the color filter used in the liquid crystal display device, the requirements for brightness, color purity, and the like are becoming higher and higher. Further, since the liquid crystal display device is used for a long period of time, the color filter is also required to have high quality in terms of resistance to heat resistance and light resistance. Furthermore, for the coloring composition used in the manufacture of a color filter, the requirements for uniformity, sensitivity, development, and pattern shape of the coating are becoming higher and higher when forming each filter segment. . In order to cope with such demands, the concentration of the pigment such as the pigment in the coloring composition is increased, and the concentration of the component of the photocurable resin or the monomer is correspondingly lowered.

Further, in order to cope with the continuous increase in the liquid crystal display device, in the manufacture of the color filter, the process is simplified and the production time is shortened.

However, increasing the concentration of the coloring material in the coloring composition to reduce the photocurable component, or shortening the ultraviolet irradiation time for the simplification of the color filter process, causes a colored coating film having poor curing. Here, the poorly colored coloring coating film refers to a colored coating film in which a sufficiently hardened portion and a portion which is not sufficiently cured are to be cured in a place to be cured. Due to poor hardening The color coating film is subjected to alkali development, and chromatic aberration occurs in a portion which is sufficiently hardened and a portion which is not sufficiently hardened.

The inventors of the present invention have attempted to solve the above problem of chromatic aberration by a conventional technique.

First, it is possible to solve the problem of whether or not the photosensitive coloring composition containing a high-sensitivity photopolymerization initiator disclosed in Japanese Laid-Open Patent Publication No. 2005-099488 can be used to solve the problem of coating a film with a small amount of photocuring component and a small amount of ultraviolet irradiation. Poor hardening. However, when a high-sensitivity photopolymerization initiator is used, the amount of the cured photocurable component is limited, and the curing is saturated, resulting in hardening failure, and it is impossible to form a cured coating film having no chromatic aberration.

Next, the photosensitive composition having alkali resistance disclosed in Japanese Laid-Open Patent Publication No. 2002-318453, which contains a specific ratio of a component of a polyfunctional (meth)acrylic monomer, has a specific ring-containing composition. A component B composed of a polymer of a hydrocarbon constituent unit, a C component composed of a monofunctional monomer, and a D component composed of at least one of a photopolymerization initiator and a photosensitizer. However, since the component B formed by the polymer contained in the photosensitive composition is not cured by ultraviolet irradiation, peeling of the coating film occurs during alkali development, and a large chromatic aberration is caused instead.

Therefore, 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 which is incapable of causing chromatic aberration of poor curing.

According to an 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, characterized in that the polymerization is carried out. The ratio of the solubility parameter M _SP of the monomer to the double bond equivalent M _DC of the polymerizable monomer M _SP /M _DC is 0.10 or less, and the solubility parameter P _SP of the transparent resin is equivalent to the double bond equivalent P _DC of the transparent resin. The ratio of the P _SP /P _DC is 0.012 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 comprising a filter segment formed of the coloring composition of the present invention on a substrate.

Best form for implementing the invention

First, the coloring composition of the present invention will be specifically described.

The colored composition of the present invention contains a polymerizable monomer having an ethylenically unsaturated double bond (hereinafter referred to as a polymerizable monomer), a transparent resin having an ethylenically unsaturated double bond, a coloring material, and an organic solvent.

Further, in the colored composition of the present invention, the ratio of the solubility parameter M _SP of the polymerizable monomer to the double bond equivalent M _DC of the polymerizable monomer M _SP /M _DC is 0.10 or less, and the solubility parameter P _SP of the transparent resin than the transparent resin of the double bond equivalent P _DC P _SP / P _DC is 0.012 or more, and the proportion of the polymerizable monomer is present from 30 to 150% by weight of the transparent resin.

The solubility parameter M _SP of the polymerizable monomer in the present invention is described in "Polymer Eng. &Sci.", Vol. 14, No. 2 (1974), pages 148 to 154. The Fedors formula is calculated by the following formula (1).

Formula (1): M _SP = (Σ △ e _i / = Σ Δv _i ) ^{1/2 In the} formula (1), Δe _i is an evaporation energy at 25 ° C attributed to an atom or a group, Δv _i is an atom Or based on the molar volume at 25 ° C.

Δe _i and Δv _i in the formula (1) are constant values given to i atoms and groups in the molecule. Representative examples of the values of Δe and Δv given to an atom or a group are shown in Table 1.

For example, the solubility parameter of the acrylate 2-hydroxyethyl ester represented by the following structural formula (2) is calculated as follows.

That is, 2-hydroxyethyl acrylate contains 1 = CH ₂ , 1 -CH=, 1 -COO-, 2 -CH ₂ -, 1 -OH (C adjacency), and ΣΔe _i It is 1030+1030+4300+1180×2+5220=13940 (cal/mol). Further, ΣΔv _i is 28.5+13.5+18+16.1×2+13=105.2 (cm ³ /mol). Therefore, the solubility parameter M _SP of 2-hydroxyethyl acrylate is (ΣΔe _i /ΣΔv _i ) ^1/2 =11.5 (cal/cm ³ ).

Further, the solubility parameter of a mixture of two or more types of polymerizable monomers is calculated by the following formula: M _SPmix = a _M1 M _SPM1 + a _M2 M _SPM2 + a _M3 M _SPM3 +. . . +a _Mn M _SPMn Here, the solubility parameter of a mixture of M _SPmix- based polymerizable monomers, the solubility parameter of M _SPM1- based polymerizable monomer 1, the solubility parameter of M _SPM2- based polymerizable monomer 2, and the M _SPM3- based polymerizability Solubility parameter of monomer 3, . . Solubility parameter of M _SPMn- based polymerizable monomer n, weight fraction of polymerizable monomer 1 in a mixture of a _M1 -based polymerizable monomers, and polymerizable monomer 2 in a mixture of a _M2- based polymerizable monomers Weight fraction, a part by weight of the polymerizable monomer 3 in a mixture of _M3 polymerizable monomers. . . a The weight fraction of the polymerizable monomer n in the mixture of the _Mn- based polymerizable monomers.

Further, the double bond equivalent of the polymerizable monomer is calculated by the following formula: <double bond equivalent of the polymerizable monomer>=<molecular weight of the polymerizable monomer>/<number of double bonds in the molecule of the polymerizable monomer > The standard for the amount of double bonds contained in one molecule of the polymerizable monomer. In the case of a compound of the same molecular weight, the smaller the value of the double bond equivalent, the greater the amount of the double bond.

Further, the double bond equivalent of a mixture of two or more kinds of polymerizable monomers is calculated by the following formula: M _DCmix = a _M1 M _DCM1 + a _M2 M _DCM2 + a _M3 M _DCM3 +. . . + _{a Mn} M DCMn double bond equivalent Here, the mixture of double bond equivalent _M DCmix based polymerizable monomer, M _DCM1 1-based polymerizable monomer, polymerizable double bond equivalent M _DCM2-based monomer _2, M DCM3 Is the double bond equivalent of the polymerizable monomer 3, . . The double bond equivalent of the M _DCMn polymerizable monomer n, the weight fraction of the polymerizable monomer 1 in the mixture of the a _M1 -based polymerizable monomers, and the polymerizable monomer 2 in the mixture of the a _M2 -based polymerizable monomers The weight fraction, the weight fraction of the polymerizable monomer 3 in the mixture of a _M3- based polymerizable monomers. . . a The weight fraction of the polymerizable monomer n in the mixture of the _Mn- based polymerizable monomers.

When the ratio M _SP /M _DC of the solubility parameter M _SP of the polymerizable monomer to the double bond equivalent M _DC of the polymerizable monomer is more than 0.1, the surface of the coating film is cured by ultraviolet irradiation, and cracks occur in the cured coating film. The M _SP /M _{DC is} preferably 0.03 or more, more preferably 0.05 or more and less than 0.07.

The double bond equivalent of the polymerizable monomer contained in the colored composition of the present invention is preferably from 120 to 350, more preferably from 150 to 300. When the double bond equivalent ratio of the polymerizable monomer is small, the surface of the coating film is hardened by ultraviolet irradiation, and cracks occur in the cured coating film. In addition, when the double bond equivalent ratio 350 of the polymerizable monomer is large, the sensitivity of the colored composition is insufficient, and the coating film is not cured even by ultraviolet rays.

The polymerizable monomer is exemplified by 2-hydroxyethyl acrylate (solubility parameter (hereinafter referred to as SP): 11.5, double bond equivalent (hereinafter referred to as 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 propylene Acid ester (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) 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), methacrylamide (SP: 13.3, DC: 85), N-hydroxyl Methyl acrylamide (SP: 15.4, DC: 101), N-methylol methacrylamide (SP: 14.5, DC: 115), acrylonitrile (SP: 11.1, DC: 53), and the like. It is also possible to use a part of the carbon chain of the aforementioned polymerizable monomer which is modified by caprolactone, ethylene oxide or propylene oxide.

The polymerizable monomer may be used alone or in combination of two or more.

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 in a full-wavelength region of 400 to 700 nm in the visible light region. More than 80%, more preferably 95% or more of the resin. The solubility parameter of the photocurable transparent resin is calculated by the Fedors formula in the same manner as the polymerizable monomer. However, in the case of a photocurable transparent resin, it is calculated from the theoretical monomer composition (mol ratio) constituting the resin as shown in the following formula.

Solubility parameter of photocurable transparent resin P _SP = Wta × SPa + Wtb × SPb + Wtc × SPc... Here, Wta: Molar fraction of monomer A, Wtb: Mohr fraction of monomer B, Wtc: The molar fraction of monomer C, . . SPa: Solubility parameter of monomer A, SPb: solubility parameter of monomer B, SPc: solubility parameter of monomer B, . .

For example, the constituent monomer of the photocurable transparent resin is 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) × (solubilization 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 a mixture of two or more types of photocurable transparent resins is calculated by the following formula: P _SPmix = a _P1 M _SPM1 + a _P2 M _SPM2 + a _P3 M _SPM3 +. . . +a _Pn M _SPMn Here, the solubility parameter of a mixture of P _SPmix- based photocurable transparent resin, the solubility parameter of P _SPS1- based photocurable transparent resin 1, and the solubility parameter of P _SPS2- based photocurable transparent resin 2, P _SPS3 The solubility parameter of the photocurable transparent resin 3, . . The solubility parameter of the M _SPSn- based photocurable transparent resin n, the weight fraction of the photocurable transparent resin 1 in the mixture of a _P1 photocurable transparent resin, and the photohardening in a mixture of a _P2 photocurable transparent resin The weight fraction of the transparent resin 2, the weight fraction of the photocurable transparent resin 3 in the mixture of a _P3- based photocurable transparent resin. . . a The weight fraction of the photocurable transparent resin n in the mixture of _Pn- based photocurable transparent resins.

In addition, the double bond equivalent of the photocurable transparent resin is calculated by the following formula: <double bond equivalent of photocurable transparent resin>=<weight average molecular weight of photocurable transparent resin>/<photocurable transparent resin 1 molecule The number of double bonds in the medium is the standard of the amount of double bonds contained in one molecule of the photocurable transparent resin. In the case of a compound of the same molecular weight, the smaller the value of the double bond equivalent, the greater the amount of the double bond.

The double bond equivalent of a mixture of two or more kinds of photocurable transparent resins is calculated by the following formula: P _DCmix = a _P1 P _DCP1 + a _P2 P _DCP2 + a _P3 P _DCP3 +. . . ₊ a _Pn P DCPn Here, a mixture of double bond equivalent based light-curing transparent resin of _P DCmix, P _DCP1-based light-curing transparent resin double bond equivalent of 1, P _DCP2-based light-curing transparent resin double bond equivalent of 2 , P _DCP3 is a double bond equivalent of photocurable transparent resin 3. . . The double bond equivalent of the P _DCPn photocurable transparent resin n, the weight fraction of the photocurable transparent resin 1 in the mixture of the a _P1 photocurable transparent resin, and the light in the mixture of the a _P2 photocurable transparent resin The weight fraction of the curable transparent resin 2, the weight fraction of the photocurable transparent resin 3 in the mixture of the a _P3 photocurable transparent resin. . . a The weight fraction of the photocurable transparent resin n in the mixture of _Pn- based photocurable transparent resins.

When the ratio _PSP /P _DC of the solubility parameter P _{SP of the} photocurable transparent resin to the double bond equivalent P _DC of the photocurable transparent resin is 0.012 or less, the photocurability of the colored composition is lowered, and even if it is irradiated with ultraviolet rays, it is coated. The film will not be sufficiently hardened. P _SP /P _{DC is} preferably 0.05 or less, more preferably 0.015 or more and 0.045 or less.

The double-bond equivalent of the photocurable transparent resin contained in the colored composition of the present invention is preferably from 200 to 800, more preferably from 300 to 700. When the double bond equivalent ratio 200 of the photocurable transparent resin is small, the surface of the coating film is hardened by ultraviolet irradiation, and cracks occur in the cured coating film. Moreover, when the double bond equivalent ratio of the photocurable transparent resin is larger than 800, the sensitivity of the sufficient coloring composition cannot be obtained, and the coating film is not sufficiently cured even when irradiated with ultraviolet rays.

As the photocurable transparent resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group, and a (meth) group having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group are used. Acrylic compound or The cinnamic acid reacts to introduce a photocrosslinkable group such as a (meth) acrylonitrile group or a styryl group into the resin of the linear polymer. Further, an acid anhydride-containing wire such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer may be used as a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate. Polymeric semi-esterification.

The photocurable transparent resin may be used alone or in combination of two or more.

In the coloring composition of the present invention, the content of the polymerizable monomer is 30 to 150% by weight of the photocurable transparent resin, and more preferably 50 to 100%. In the coloring composition of the present invention, the polymerizable single system achieves the task of curing the main body, and the photocurable transparent resin achieves the task of curing the curing. The photocurable transparent resin itself has a small effect on photocuring as compared with a polymerizable monomer. On the other hand, the polymerizable monomer is hardened by light itself, and the amount thereof is as described above. The photocurable transparent resin and the polymerizable monomer are preferably contained in a well-balanced manner.

When the coating film formed using the colored composition of the present invention is irradiated with ultraviolet rays, the ethylenically unsaturated double bond of the photocurable transparent resin is used as a starting point to promote polymerization of the polymerizable monomer and ultraviolet irradiation. Part of the coating system does not suffer from hardening and is fully hardened. When the amount of the polymerizable monomer is more than 150% by weight of the photocurable transparent resin, the photocurable transparent resin which is a polymerization starting point of the polymerizable monomer is small, and the polymerizable monomer is not sufficiently cured, which is not preferable. In addition, when the amount is less than 30%, the polymerizable monomer is sufficiently cured. However, since the absolute amount of the polymerizable monomer is reduced, the curing of the coating film is 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, per 100 parts by weight of the coloring material.

As the coloring material contained in the colored composition of the present invention, two or more kinds of organic or inorganic pigments may be used alone or in combination. Among the pigments, pigments having high color rendering properties and high heat resistance are preferred, and pigments having high heat decomposition resistance are generally used, and organic pigments are usually used.

Hereinafter, specific examples of the organic pigment which can be preferably used in the colored composition of the present invention are shown by color index (C.I.).

For the red colored composition for forming the red filter segment, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81 can be used. : 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 Red pigments of 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, and the like. In the red coloring composition, a yellow pigment or an orange pigment may be used in combination.

For the yellow colored composition for forming the yellow filter segment, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20 can be used. , 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 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 Yellow pigments of 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, and the like.

For the orange colored composition for forming the orange filter segment, for example, an orange pigment of C.I. Pigment Orange 36, 43, 51, 55, 59, 61 or the like can be used.

For the green coloring composition for forming the green filter segment, for example, a green pigment of C.I. Pigment Green 7, 10, 36, 37 or the like can be used. In the green coloring composition, a yellow pigment may be used in combination.

For the blue colored composition for forming the blue filter segment, for example, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 can be used. , 64, etc. blue pigment. In the blue coloring composition, a violet pigment of C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, or the like can be used in combination.

For the cyan coloring composition for forming the cyan filter segment, for example, a blue pigment of C.I. Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81, or the like can be used.

For the magenta coloring composition for forming the magenta filter segment, for example, a violet pigment and a red pigment of C.I. Pigment Violet 1, 19, C.I. Pigment Red 144, 146, 177, 169, 81 and the like can be used. In the magenta coloring composition, a yellow pigment may be used in combination.

Further, examples of the inorganic pigment include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, and cobalt green. Amber, titanium black, synthetic iron, oxidation Metal oxide powder such as titanium or iron oxide, metal sulfide powder, or metal powder. In order to obtain a balance between chroma and lightness, and to ensure good coatability, sensitivity, development, and the like, an inorganic pigment is used in combination with an organic pigment.

In the coloring composition of the present invention, a dye may be contained in the range of not reducing heat resistance for coloring.

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, and n-amyl 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,N-dimethylformamide, 1,2,3-trichloropropane, o-chlorotoluene, o-xylene, m-xylene, 3-methoxy-3-methyl 1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutylketone, 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 II Ethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate Acid ester, 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, γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone, o-chloro Toluene, o-diethyl Benzobenzene, m-diethylbenzene, p-diethylbenzene, o-dichlorobenzene, m-dichlorobenzene, n-butylbenzene, t-butylbenzene, t-butylbenzene, cyclohexanol, methylcyclohexane Alcohol, etc. These may be used alone or in combination of two or more. The organic solvent may be used in an amount of from 800 to 4,000 parts by weight, preferably from 1,000 to 2,500 parts by weight, per 100 parts by weight of the pigment in the colored composition.

A photopolymerization initiator is added to the colored composition of the present invention.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl) can be used. -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl An acetophenone-based photopolymerization initiator such as 1-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, etc. Benzoin photoinitiator, benzophenone, benzhydrylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone a benzophenone-based photopolymerization initiator such as a ketone or 4-benzylidene-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, Thiophenone photopolymerization initiator such as isopropyl thioxanthone or 2,4-diisopropyl thioxanthone, 2,4,6-trichloro-s-three 2-phenyl-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three , 2-piperidin-4,6-bis(trichloromethyl)-s-three 2,4-bis(trichloromethyl)-6-styryl-S-three 2-(naphthoquinone-1-yl)-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxy-naphthoquinol-1-yl)-4,6-bis(trichloromethyl)-s-three 2,4-trichloromethyl-(piperidinyl)-6-three 2,4-trichloromethyl (4'-methoxystyryl)-6-three Three A photopolymerization initiator, a borate ester photopolymerization initiator, an oxazole photopolymerization initiator, an imidazole photopolymerization initiator, 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, per 100 parts by weight of the pigment in the colored composition.

The photopolymerization initiator may be used singly or in combination of two or more kinds, but may be used together as a sensitizer α-methoxyl ester, mercaptophosphine oxide, methylphenylglyoxylate, benzoin , 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4'-diethylisoindole, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl A compound such as ketone or 4,4'-diethylaminobenzophenone. The sensitizer may be used in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator in the colored composition.

In the coloring composition of the present invention, one or two or more kinds of coloring materials and the above-mentioned polymerizable property can be used by various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and a vertical mill. The monomer and the photopolymerization initiator are produced by finely dispersing in the photocurable transparent resin and the organic solvent. In addition, a coloring composition containing two or more types of coloring materials may be produced by mixing each coloring material in a finely dispersed manner in the photocurable transparent resin and the organic solvent. When the pigment of the coloring material is dispersed in the photocurable transparent resin and the organic solvent, a dispersing aid such as a resin type pigment dispersant, a surfactant, or a pigment derivative may be appropriately contained. The dispersing aid is excellent in the dispersion of the pigment, and has a large effect of preventing re-agglomeration of the pigment after dispersion. When the pigment is dispersed in the photocurable transparent resin and the organic solvent to form a coloring composition, the dispersing aid is used. This coloring composition can obtain a color filter excellent in transparency.

The resin-type pigment dispersant has a pigment affinity site having a property of adsorbing on a pigment and a site compatible with a pigment carrier, and has a function of adsorbing on a pigment to stabilize the dispersion of the pigment carrier of the pigment. As the resin type pigment dispersant, specifically, a polycarboxylate such as a polyurethane or a polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, or a polycarboxylate can be used. a salt, a polycarboxylic acid alkylamine salt, a polyoxyalkylene oxide, a long chain polyamino valerate, a hydroxyl group-containing polycarboxylate, or a modified product thereof, from poly(lower alkyleneimine) An oily dispersant such as guanamine or a salt thereof formed by a reaction with a polyester having a free carboxyl group; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, benzene Water-soluble resin or water-soluble polymer compound such as ethylene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide addition A compound, a phosphate ester, etc. can be used individually or in mixture of 2 or more types.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyl diphenyl ether disulfonate. Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene alkylene Anionic surfactant such as ether ether phosphate; polyoxyethylene ether ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan single a nonionic surfactant such as stearate or polyethylene glycol monolaurate; a cationic surfactant such as an alkyl 4-grade ammonium salt or such an ethylene oxide adduct; An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as dimethylaminoacetate or betaine may be used alone or in combination of two or more.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also contains a pale yellow aromatic polycyclic compound such as a naphthalene or an anthracene which is not generally called a pigment. As a pigment derivative, it is described in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, JP-A-5-9469, and the like. These may be used alone or in combination of two or more types.

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, per 100 parts by weight of the coloring material.

In the colored composition of the present invention, in order to control the solubility or resistance to the developing solution, a non-photosensitive transparent resin may be contained. The non-photosensitive transparent resin does not have an ethylenically unsaturated double bond, and the transmittance in the entire wavelength range of 400 to 700 nm in the visible light region is preferably 80% or more, and more preferably 95% or more. Such a non-photosensitive transparent resin contains a thermoplastic resin and a thermosetting resin, and these may be used alone or in combination of two or more types.

Examples of the non-photosensitive thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and poly Vinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polybutylene Alkene, polyimine resin, and the like. Also, as non-photosensitive Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

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, per 100 parts by weight of the coloring material.

Further, in the colored composition of the present invention, a storage stabilizer may be contained in order to stabilize the time-dependent viscosity of the composition. Examples of the storage stabilizer include hydroquinone, methylhydroquinone, 2,5-di-tert-butylhydroquinone, tert-butylhydroquinone, tert-butyl-β-benzoquinone, and tert-butyl group. a hydroquinone compound such as hydroquinone or 2,5-diphenyl-p-benzoquinone; a 4-grade ammonium chloride such as benzyltrimethyl chloride or diethylhydroxylamine; an organic acid such as lactic acid or oxalic acid; Phosphine oxidation of phosphine compounds such as methyl ether, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. a phosphite compound such as a compound, triphenyl phosphite or tridecyl phenyl phosphite; or a third butyl pyrocatechol. The stabilizer is stored in an amount of 0.1 to 10 parts by weight for 100 parts by weight of the coloring matter in the colored composition.

Further, in order to improve the adhesion to the substrate, an adhesion improver such as a decane coupling agent may be contained.

Examples of the decane coupling agent include vinyl decane such as vinyl tris(β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane, and γ-methyl propylene oxime. (meth) acrylonitrile decane such as propyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, --(3,4-epoxycyclohexyl)methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl Epoxy decane, N-β (aminoethyl) such as methyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxy propyl triethoxy decane Γ-aminopropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-Aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxy An alkyl decane such as decane, a sulfodenomene such as γ-mercaptopropyltrimethoxydecane or γ-mercaptopropyltriethoxydecane. The decane 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 color filter used in the coloring composition.

The coloring composition of the present invention preferably removes coarse particles of 5 μm or more by means of centrifugation, a sintered filter, a membrane filter, etc., preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more. And the dust that is mixed in.

Further, in the colored composition of the present invention, a uniform coating film can be obtained in order not to cause uneven coating, and it is preferable that the viscosity measured at 25 ° C using an E-type viscometer at a number of revolutions of 20 rpm becomes 10 mPa. s The following ways to adjust, better to become 1mPa. s above and 8mPa. s The following methods are adjusted.

The colored composition of the present invention can be prepared in the form of a solvent development type or an alkali development type colored photoresist.

Next, the description will be made with the filter formed by the coloring composition of the present invention. Segment color filter.

The color filter is formed on the transparent or reflective substrate to have at least two colors selected from R (red), G (green), B (blue), Y (yellow), M (magenta), and C (cyan). Filter segment. The filter segments of the respective colors can be formed by the lithography method using the coloring composition of the present invention.

As the transparent substrate, a resin plate such as a glass plate, polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used.

As the reflective substrate, an aluminum, silver, silver/copper/palladium alloy thin film or the like can be formed on the crucible or the transparent substrate.

When the filter segments of the respective colors are formed by the lithography method, the coloring composition prepared by the solvent development type or the alkali development type colored photoresist is sprayed or spin-coated, slit-coated, and rolled. The coating method such as the coating method is applied onto the substrate so that the dried film thickness is 0.2 to 5 μm. The film which has been dried as needed is subjected to ultraviolet light exposure by a mask having a predetermined pattern which is provided in contact with or not in contact with the film. Then, by immersing in a solvent or an alkali developing solution, spraying or the like, the developing liquid is sprayed to remove the unhardened portion, and a desired pattern is formed, and the same operation is repeated for the other colors to produce a color filter. Further, in order to promote polymerization of the colored photoresist, heating may be applied as needed. By the lithography method, a color filter having higher precision than the printing method can be manufactured.

As the development processing method, a shower development method, a spray development method, an impregnation (immersion) development method, a shallow pit (full liquid) development method, or the like can be used.

Furthermore, in order to improve the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyethylene may be applied after the colored photo-resist material is coated and dried. The enol or water-soluble acrylic resin is coated and dried to form a film that prevents polymerization failure due to oxygen, and then exposed to ultraviolet light.

In the following, the present invention will be described in more detail by way of examples, but the following examples are not intended to limit the scope of the invention. In addition, the "parts" in the examples mean "parts by weight".

Synthesis Example 1

560 parts of cyclohexanone was placed in a reaction vessel, and while the container was filled with nitrogen gas, it was heated to 80 ° C, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, and 45.0 parts were dropped at the same temperature for 1 hour. A mixture of n-butyl methacrylate, 47.0 parts of glycerin monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was subjected to polymerization.

After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was added and dissolved in 55 parts of cyclohexanone, and the reaction was further continued at 80 ° C for 1 hour to obtain a copolymer solution.

Next, to 338 parts of the obtained copolymer solution, 32.0 parts of 2-methylpropenylethyl isocyanate, 0.4 part of dibutyltin laurate, and 120.0 parts of cyclohexanone were added dropwise at 70 ° C for 3 hours. mixture.

After cooling to room temperature, about 2 g of the obtained photocurable transparent resin solution was sampled, and dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured. Based on the measured value, the previously synthesized photocurable transparent resin was used. In the solution, cyclohexanone was added so as to have a nonvolatile content of 20% by weight to prepare a photocurable transparent resin solution A. The photocurable transparent resin obtained had a weight average molecular weight of 20,000, a double bond equivalent of 470, and a solubility parameter of 11.0.

Synthesis Example 2

520 parts of cyclohexanone was placed in a reaction vessel, and while the container was filled with nitrogen gas, it was heated to 80 ° C, and 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, and 63.0 parts were dropped at the same temperature for 1 hour. A mixture of 2-hydroxyethyl methacrylate, 66.0 parts of glycerin monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was subjected to a polymerization reaction.

After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was added and dissolved in 70 parts of cyclohexanone, and the reaction was further continued at 80 ° C for 1 hour to obtain a copolymer solution.

Next, to 220 parts of the obtained copolymer solution, 56.0 parts of 2-methylpropenylethyl isocyanate, 0.4 part of dibutyltin laurate, and 220.0 parts of cyclohexanone were added dropwise at 70 ° C for 3 hours. a mixture.

After cooling to room temperature, cyclohexanone was added so that the nonvolatile content was 20% by weight, and the photocurable transparent resin solution B was prepared, as in the case of the synthesis example 1. The photocurable transparent resin obtained had a weight average molecular weight of 20,000, a double bond equivalent of 270, and a solubility parameter of 11.0.

Synthesis Example 3

480 parts of cyclohexanone was placed in a reaction vessel, and while the container was filled with nitrogen gas, it was heated to 80 ° C, and 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, and 16.0 parts were added dropwise at the same temperature for 1 hour. A mixture 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 subjected to a polymerization reaction.

After the completion of the dropwise addition, after further reacting at 80 ° C for 3 hours, 1.0 part of the mixture was added. The azobisisobutyronitrile was dissolved in 80 parts of cyclohexanone, and the reaction was further continued at 80 ° C for 1 hour to obtain a copolymer solution.

Next, 445 parts of the obtained copolymer solution were subjected to dropwise addition of 14.0 parts of 2-methylpropenylethyl isocyanate, 0.4 part of dibutyltin laurate, and 55.0 parts of cyclohexanone at 70 ° C for 3 hours. a mixture.

After cooling to room temperature, cyclohexanone was added so that the nonvolatile content was 20% by weight, and the photocurable transparent resin solution C was prepared. The photocurable transparent resin obtained had a weight average molecular weight of 20,000, a double bond equivalent of 1,000, and a solubility parameter of 10.8.

Example 1

The mixture of the following composition was uniformly stirred and mixed, and then glass beads having a diameter of 1 mm were used, and dispersed by a sand mill for 5 hours, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.

Composition of the mixture (copper phthalocyanine dispersion):

Next, the mixture of the following composition was stirred and mixed to be uniform, and then filtered with a filter of 1 μm to obtain a colored composition adjusted as a blue photoresist. The composition of the colored composition (weight ratio when the total amount of the colored composition was 100) is shown in Table 2.

Composition of the mixture (coloring composition):

Examples 2 to 9 and Comparative Examples 1 to 7

The composition of the pigment, the dispersant, the photocurable transparent resin solution, and the solvent was changed to the ratio shown in Table 2 (the weight ratio when the total amount of the pigment dispersion was 100), and the pigment dispersion of each color was obtained in the same manner as in Example 1. body.

Next, the composition of the pigment dispersion, the photocurable transparent resin solution, the polymerizable monomer, the photopolymerization initiator, the sensitizer, the organic solvent, and the leveling agent was changed to those shown in Tables 3-1 and 3-2. A coloring composition adjusted as a photoresist of each color was obtained in the same manner as in Example 1 except that the ratio (the weight ratio when the total amount of the coloring composition was 100) was obtained.

In Table 2, PB15:6=ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6) ("Heliogenblue L-6700F" manufactured by BASF); PR254 = diketopyrrolopyrrole pigment (CI Pigment Red 254) ) (Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) PR177 = lanthanide pigment (CI Pigment Red 177) ("Cromophtal Red A2B" manufactured by Ciba Specialty Chemicals Co., Ltd.); PY199 = lanthanide pigment (CI Pigment Yellow 199) (Cromophtal Yellow GT-AD) manufactured by Ciba Specialty Chemicals Co., Ltd.; PG36 = Copper Oxide Cyanine Pigment (CI Pigment Green 36) ("Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.) ; PY150 = monoazo pigment (CI Pigment Yellow 150) ("Fanchon Fast Yellow Y-5688" manufactured by Lanxess Co., Ltd.) dispersant = "Soluspass 20000" resin manufactured by Lubrizol Co., Ltd. A = photocurable transparent obtained in Synthesis Example 1. Resin solution A; Resin B = photocurable transparent resin solution B obtained in Synthesis Example 2; Resin C = photocurable transparent resin solution C obtained in Synthesis Example 3.

In Tables 3-1 and 3-2, monomer A = caprolactone-modified trimethylolpropane triacrylate ("Ebecryl 2047" manufactured by Daicel-Cytec Co., Ltd., solubility parameter: 10.6, double bond equivalent: 201) Monomer B = ethylene oxide modified trimethylolpropane triacrylate ("Aronix M-350" manufactured by Toagosei Co., Ltd., solubility parameter: 10.1, double bond equivalent: 143); monomer C = trishydroxyl Propane triacrylate ("NKester A-TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd., solubility parameter: 10.5, double bond equivalent: 99); Resin A = photocurable transparent resin solution A obtained in Synthesis Example 1; Resin B = Photocurable transparent resin solution B obtained in Synthesis Example 2; Resin C = photocurable transparent resin solution C obtained in Synthesis Example 3; Photopolymerization initiator = "Irgacure 907" sensitizer manufactured by Ciba Specialty Chemicals Co., Ltd. "EAB-F" manufactured by Toya Chemical Co., Ltd.; leveling agent = "BYK-323" manufactured by BYK Chemical Co., Ltd.

Each of the color resists obtained in Examples 1 to 9 and Comparative Examples 1 to 7 was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm thick by a spin coater to form a coating film having a thickness of 2.0 μm. Next, after prebaking at 70 ° C for 20 minutes, ultraviolet exposure of 100 mJ/cm ² was performed. The spectral transmittance of the obtained photocured film was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.), and then immersed in a 0.25% aqueous sodium hydroxide solution. After immersing for 2 minutes, the spectroscopic spectrophotometer was again used, and the spectral transmittance was measured to calculate the color difference ΔEab. Further, after immersing in a 0.25% sodium hydroxide aqueous solution for 2 minutes, the development of the stain was observed using an optical microscope, and the level was 4 ((: no visible stain was observed, ○: although a little bit, but seen It is evaluated by a light stain, △: a pale stain on the whole, and a large stain on the whole. The results are shown in Table 4.

The color difference ΔEab before and after the immersion of the aqueous sodium hydroxide solution was compared with the hardened coating film formed by the coloring compositions obtained in Comparative Examples 1 to 7 by the cured coating film formed of the colored compositions obtained in Examples 1 to 6. Small, for the good results of the occurrence of no visible stains.

Further, when the amount of the cured coating film produced by the coloring compositions obtained in Examples 7 to 9 was close to the preferred range, the color difference ΔEab was larger than that of the optimum example 9, and the development of the stain was observed. Compared with Example 9, it was also a slightly observed result.

As described above, since the colored composition of the present invention is sufficiently cured by ultraviolet irradiation, the cured coating film formed by the colored composition of the present invention exhibits sufficient resistance to the alkali developing solution. As a result, the in-plane color difference of the filter segment of the color filter becomes no, and a good liquid crystal display is obtained. Display device. A stable liquid crystal display device is obtained by reducing the cost of the production line or increasing the throughput of the material due to a decrease in the defective rate of the production line, and an excellent effect in the market of the liquid crystal display device which is required to increase the demand for the rapid growth.

Claims (4)

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, characterized in that the solubility parameter of the polymerizable monomer is M _SP The ratio M _SP /M _DC of the double bond equivalent M _DC of the polymerizable monomer is 0.10 or less, and the ratio P _SP /P _DC of the solubility parameter P _{SP of the} transparent resin to the double bond equivalent P _DC of the transparent resin is 0.012. The content of the polymerizable monomer is 30 to 150% by weight of the transparent resin. The coloring composition of claim 1, wherein the polymerizable monomer has a double bond equivalent M _{DC of} from 120 to 350. The colored composition of claim 1 or 2, wherein the transparent resin has a double bond equivalent P _DC of 200 to 800. A color filter comprising a filter segment formed by the colored composition of any one of claims 1 to 3 on a substrate.