KR101431502B1 - Coloring compositions and color filters using them - Google Patents

Abstract

The coloring composition contains 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 (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 0.10 or less, and the transparency to the double bond equivalent (P _DC ) The ratio (P _SP / P _DC ) of the solubility parameter (P _SP ) of the resin is 0.012 or more. The polymerizable monomer is contained in an amount of 30 to 150% of the weight of the transparent resin. The color filter comprises a filter segment formed from the coloring composition on a substrate.

Coloring composition, color filter, transparent resin, filter segment, monitor, liquid crystal display device.

Description

COLOR COMPOSITION AND COLOR FILTER USING THE SAME [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition and a color filter which are suitably used in the production of a color filter constituting a color liquid crystal display device, a color image pickup tube device or the like.

2. Description of the Related Art In recent years, liquid crystal display devices have been applied to television monitor applications, PC monitor applications, and mobile applications. For a color filter used in a liquid crystal display device, a demand level for brightness, color purity, and the like is increasing for improving color reproducibility. In addition, since a liquid crystal display device is used for a long period of time, a color filter is required to have a high quality with respect to resistance to heat and light. In addition, with respect to the coloring composition used in the production of the color filter, the level required for coating uniformity, sensitivity, developability and pattern shape when forming each color filter segment is also increasing. In order to meet these demands, the concentration of the coloring agent such as pigment in the coloring composition is increased, and the concentration of the component of the photocurable resin or the monomer is correspondingly lowered.

In addition, in order to cope with the ever-increasing demand of the liquid crystal display device, the production time is shortened by the simplification of the manufacturing process of the color filter.

However, in order to shorten the photo-curable component by increasing the concentration of the coloring agent in the coloring composition and to shorten the ultraviolet irradiation time in order to simplify the manufacturing process of the color filter, a colored coating film with poor curing results. Here, the colored coating film with poor curing refers to a colored coating film in which a portion that is sufficiently cured in a portion to be cured and a portion in which curing is insufficient are mixed. Alkali development of the cured poorly colored coating film causes a color difference in a part that is sufficiently cured and a part where curing is insufficient.

The inventors of the present invention have attempted to solve the above-mentioned problem of color difference by the prior art.

First, it was examined whether a photosensitive coloring composition containing a high-sensitivity photopolymerization initiator disclosed in Japanese Patent Application Laid-Open No. 2005-099488 could be used to solve the problem of hardening of a coating film with a small amount of photo-curing component and a small amount of ultraviolet radiation. However, even when a high-sensitivity photopolymerization initiator is used and the content thereof is increased, the amount of the photo-curing component to be cured is limited, so that the curing is saturated and the cured film having no color difference due to the curing defect has not been obtained.

Next, the B component composed of the A component composed of the polyfunctional (meth) acrylic monomer and the polymer having the constitutional unit containing the specific cyclic hydrocarbon, which is disclosed in Japanese Patent Application Laid-Open No. 2002-318453, and the B component composed of the monofunctional monomer C component and at least one of a photopolymerization initiator and a photosensitizer in a specific ratio in addition to the alkali-soluble photosensitive composition. However, since the B component composed of the polymer contained in the photosensitive composition is not cured by ultraviolet irradiation, coating film peeling occurs due to alkali development, and a large color difference is produced on the contrary.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a color filter comprising a colored composition having high curability by ultraviolet ray and a filter segment in which a color difference due to a curing defect is not recognized.

According to one 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, the polymerizable solubility parameter of the monomer (and the 0.10 ratio (M _SP / M _DC) of M _SP), the solubility parameter of the transparent resin to the double bond equivalent weight (P _DC) of the transparent resin for the M _DC) ( the ratio (P _SP / P _DC) is more than 0.012 of P _SP), a coloring composition, characterized in that the polymerizable monomer is contained in an amount of from 30 to 150% of the weight of the transparent resin is provided.

According to another aspect of the present invention, there is provided a color filter having a filter segment formed from the coloring composition of the present invention on a substrate.

(Best Mode for Carrying Out the Invention)

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

The coloring 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 agent, and an organic solvent.

In the coloring composition of the present invention, 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 0.10 or less, The ratio (P _SP / P _DC ) of the solubility parameter (P _SP ) of the transparent resin to the bonding equivalent (P _DC ) is 0.012 or more, and the polymerizable monomer is present in a proportion of 30 to 150% .

The solubility parameter (M _SP ) of the polymerizable monomer in the present invention is described in "Polymer Eng. &Sci." Vol. 14, No. 2 (1974), p. 154, i.e., the following formula (1).

(1): M _SP = (ΣΔe _i / ΣΔv _i ) ^1/2

In the formula (1),? E _i is the evaporation energy at 25 ° C attributed to the atom or group, and? V _i is the molar volume of the atom or group at 25 ° C.

Formula (1) in Δe _i and Δv _i is a given constant value, and i groups of atoms in the molecule. Table 1 shows representative examples of numerical values of Δe and Δv given for atoms or groups.

For example, the solubility parameter of 2-hydroxyethyl acrylate represented by the following formula (1) is calculated as follows.

That is, 2-hydroxyethyl acrylate contains one ═CH ₂ , one -CH═, one -COO-, two -CH ₂ -, and one -OH (C adjacent) The ΣΔe _i is 1030 + 1030 + 4300 + 1180 × 2 + 5220 = 13940 (cal / mol). ? V _i is 28.5 + 13.5 + 18 + 16.1 x 2 + 13 = 105.2 (cm ³ / mol). Therefore, the solubility parameter (M _SP ) of 2-hydroxyethyl acrylate is (?? E _i /? V _i ) ^1/2 = 11.5 (cal / cm ³ ).

And the solubility parameter of the mixture of two or more kinds of polymerizable monomers is represented by the following formula:

_SPmix M = a M _{SPM1 M1} + _M2 a _SPM2 M + a _M3 + ... M _SPM3 + _{Mn Mn} M _SPMn

Lt; / RTI >

here,

M _SPmix is the solubility parameter of the mixture of polymerizable monomers,

M _SPM1 is the solubility parameter of the polymerizable monomer 1,

M _SPM2 is the solubility parameter of the polymerizable monomer 2,

M _SPM3 is the solubility parameter of the polymerizable monomer 3,

...

M _SPMn is the solubility parameter of the polymerizable monomer n,

a _M1 is the weight fraction of the polymerizable monomer 1 in the mixture of polymerizable monomers,

a _M2 is the weight fraction of the polymerizable monomer 2 in the mixture of polymerizable monomers,

a _M3 is the weight fraction of polymerizable monomer 3 in the mixture of polymerizable monomers,

...

a _Mn is the weight fraction of the polymerizable monomer n in the mixture of polymerizable monomers.

The double bond equivalent of the polymerizable monomer is represented by the following formula:

<Double bond equivalent of polymerizable monomer> = <molecular weight of polymerizable monomer> / <number of double bonds in one molecule of polymerizable monomer>

And is a measure of the amount of double bonds contained in one molecule of the polymerizable monomer. When a compound having the same molecular weight is used, the smaller the value of the double bond equivalent is, the more the amount of the double bond is.

The double bond equivalent of a mixture of two or more kinds of polymerizable monomers is represented by the following formula:

M _DCmix = a _M1 M _DCM1 + a _M2 M _DCM2 + a _M3 M _DCM3 + ... + a _Mn M _DCMn

Lt; / RTI &gt;

here,

M _DCmix is the double bond equivalent of the mixture of polymerizable monomers,

M _DCM1 is the double bond equivalent of polymerizable monomer 1,

M _DCM2 is the double bond equivalent of the polymerizable monomer 2,

M _DCM3 is the double bond equivalent of the polymerizable monomer 3,

...

M _DCMn is the double bond equivalent of the polymerizable monomer n,

a _M1 is the weight fraction of the polymerizable monomer 1 in the mixture of polymerizable monomers,

a _M2 is the weight fraction of the polymerizable monomer 2 in the mixture of polymerizable monomers,

a _M3 is the weight fraction of polymerizable monomer 3 in the mixture of polymerizable monomers,

...

a _Mn is the weight fraction of the polymerizable monomer n in the mixture of 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 greater than 0.1, curing of the surface of the coating film proceeds by ultraviolet irradiation, Cracks are formed in the cured coating film. 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 coloring composition of the present invention is preferably 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 is hardened by irradiation with ultraviolet rays, and a crack or the like may occur 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 when irradiated with ultraviolet rays.

As the polymerizable monomer, 2-hydroxyethyl acrylate (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-hydroxypropylmethacrylate (SP: 10.7, DC: 143), cyclohexyl methacrylate , DC: 154), cyclohexyl methacrylate (SP: 9.2, DC: 168), polyethylene glycol diacrylate (SP: 9.9, DC: 151), polyethylene glycol dimethacrylate ), Pentaerythritol triacrylate (SP: 12.2, DC: 99), pentaerythritol trimethacrylate (SP: 11.6, DC: 113), trimethylolpropane triacrylate (SP: , Trimethylolpropane trimethacrylate (SP: 11.4, DC: 113), dipentaerythritol hexaacrylate (SP: 10.8, DC: 97), dipentaerythritol hexamethacrylate Tricyclodecanyl methacrylate (SP: 11.0, DC: 98), melamine acrylate (SP: 11.3, DC: : Acrylic acid ester such as melamine methacrylate (SP: 10.9, DC: 163), epoxy acrylate (SP: 8.7, DC: 295), epoxy methacrylate (SP: 8.6, DC: 309) Methacrylic acid (SP: 10.7, DC: 86), styrene (SP: 7.9, DC: 104), vinyl acetate (SP: 8.9, DC: 86) (SP: 14.2, DC: 71), methacrylic acid (SP: 13.3, DC: 85), N-hydroxymethylacrylamide Methacrylamide (SP: 14.5, DC: 115), acrylonitrile (SP: 11.1, DC: 53) It is also possible to use those in which a part of the carbon chain of the polymerizable monomer is modified with caprolactone, ethylene oxide or propylene oxide.

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

The transparent resin having an ethylenically unsaturated double bond in the present invention (hereinafter referred to as a photo-curable transparent resin) has an ethylenically unsaturated double bond and has a transmittance of preferably 80 %, More preferably at least 95%. The solubility parameter of the photo-curable transparent resin is calculated by Fedors' formula as the polymerizable monomer. However, in the case of a photocurable transparent resin, it is calculated from the theoretical monomer composition (molar ratio) constituting the resin represented by the following formula.

Solubility parameter (P _SP ) of the photocurable transparent resin = Wta x SPa + Wtb x SPb + Wtc x SPc ...

here,

Wta: the mole fraction of monomer A,

Wtb: the mole fraction of monomer B,

Wtc is the mole fraction of monomer C,

...

SPa is the solubility parameter of monomer A,

SPb: Solubility parameter of monomer B,

SPc is the solubility parameter of monomer C,

...

For example, when 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 mole fraction of methacrylic acid) x (the solubility parameter of methacrylic acid) + (the mole fraction of methyl methacrylate) 占 (the solubility parameter of methyl methacrylate) = (70/86) / /86+30/100)=10.7+(30/100)/(70/86+30/100)9.3=10.32.

The solubility parameter of the mixture of two or more types of photocurable transparent resins is represented by the following formula:

_SPmix P = _P1 M _SPM1 a + a + a _SPM2 M _{P2 P3 SPM3} M + ... + a _Pn M _SPMn

Lt; / RTI &gt;

here,

P _SPmix is the solubility parameter of the mixture of photo-curable transparent resins,

P _SPS1 is a solubility parameter of the photocurable transparent resin 1,

P _SPS2 is the solubility parameter of the photocurable transparent resin 2,

P _SPS3 is a solubility parameter of the photocurable transparent resin 3,

...

M _SPSn is the solubility parameter of the photocurable transparent resin n,

a _P1 is the weight fraction of the photocurable transparent resin 1 in the mixture of the photocurable transparent resin,

a _P2 is a weight fraction of the photocurable transparent resin 2 in the mixture of the photocurable transparent resin,

a _P3 is the weight fraction of the photocurable transparent resin 3 in the mixture of the photocurable transparent resin,

...

and a _Pn is a weight fraction of the photo-curable transparent resin n in the mixture of the photo-curable transparent resin.

The double bond equivalent of the photo-curable transparent resin is represented by the following formula:

<Double bond equivalent of photocurable transparent resin> = <Weight average molecular weight of photocurable transparent resin> / <Number of double bonds in one photocurable transparent resin>

And is a measure of the amount of double bonds contained in one molecule of the photo-curable transparent resin. When a photocurable transparent resin having the same molecular weight is used, the smaller the value of the double bond equivalent is, the more the amount of the double bond is.

The double bond equivalent of a mixture of two or more types of photocurable transparent resins is represented by the following formula:

P _DCmix = a _P1 P _DCP1 + a _P2 P _DCP2 + a _P3 P _DCP3 + ... + a _Pn P _DCPn

Lt; / RTI &gt;

here,

P _DCmix is the double bond equivalent of a mixture of photo-curable transparent resins,

P _DCP1 is the double bond equivalent of the photocurable transparent resin 1,

P _DCP2 is the double bond equivalent of the photocurable transparent resin 2,

P _DCP3 is the double bond equivalent of the photocurable transparent resin 3,

...

P _DCPn is the double bond equivalent of the photocurable transparent resin n,

a _P1 is the weight fraction of the photocurable transparent resin 1 in the mixture of the photocurable transparent resin,

a _P2 is a weight fraction of the photocurable transparent resin 2 in the mixture of the photocurable transparent resin,

a _P3 is the weight fraction of the photocurable transparent resin 3 in the mixture of the photocurable transparent resin,

...

and a _Pn is a weight fraction of the photo-curable transparent resin n in the mixture of the photo-curable transparent resin.

When the ratio (P _SP / P _DC ) of the solubility parameter (P _SP ) of the photocurable transparent resin to the double bond equivalent (P _DC ) of the photo-curable transparent resin is 0.012 or less, the photo- Even if ultraviolet rays are irradiated, the coating film is not sufficiently cured. 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 coloring composition of the present invention is preferably 200 to 800, more preferably 300 to 700. When the double bond equivalent of the photo-curable transparent resin is less than 200, the surface of the coating film is hardened by irradiation with ultraviolet rays, and a crack or the like may occur in the cured coating film. When the double bond equivalent of the photo-curable transparent resin is greater than 800, sufficient coloring composition sensitivity can not be obtained, and even if ultraviolet light is irradiated, the coating film is not sufficiently cured.

As the photo-curable transparent resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group or a cinnamic acid is reacted with a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, , A styryl group, and other photo-crosslinkable groups are introduced into the linear polymer. The linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or? -Olefin-maleic anhydride copolymer is reacted with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) It is also used.

The photo-curable transparent resin may be used singly or as a mixture of two or more kinds.

In the coloring composition of the present invention, the content of the polymerizable monomer is preferably 30 to 150%, and more preferably 50 to 100% of the weight of the photocurable transparent resin. In the coloring composition of the present invention, the polymerizable monomer serves as a main curing agent, and the photo-curable transparent resin serves as a curing aid. The photo-curable transparent resin itself has little influence on the photo-curing as compared with the polymerizable monomer, while the polymerizable monomer itself cures with light, so the amount thereof is defined as described above. It is preferable that the photo-curable transparent resin and the polymerizable monomer are contained in a balanced manner.

When the coating film formed by using the coloring composition of the present invention is irradiated with ultraviolet rays, the polymerization of the polymerizable monomer is accelerated with the ethylenically unsaturated double bond of the photo-curable transparent resin as the starting point, and the entire coating film, It is sufficiently cured without causing defects. When the amount of the polymerizable monomer exceeds 150% by weight of the photocurable transparent resin, the amount of the photo-curable transparent resin which is the starting point of the polymerization of the polymerizable monomer is small and the polymerizable monomer is not sufficiently cured. If it is less than 30%, the polymerizable monomer sufficiently cures, but the absolute amount of the polymerizable monomer is reduced, 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, per 100 parts by weight of the coloring agent.

As the coloring agent contained in the coloring composition of the present invention, organic or inorganic pigments may be used singly or in combination of two or more kinds. Among the pigments, pigments having a high coloring property and a high heat resistance, particularly a pigment having a high heat decomposability, are preferable, and organic pigments are usually used.

Specific examples of organic pigments that can be preferably used in the coloring composition of the present invention are represented by color index (CI) numbers below.

Red coloring compositions for forming red filter segments include, for example, C.I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 217, 228, 227, 228, 240, 246, 254, 255, 264, 272 can be used. A yellow pigment and an orange pigment may be used in combination in the red coloring composition.

The yellow coloring composition for forming the yellow filter segment includes, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10,12, 13,14,15,16,17,18,20,24,31,32,34,35,35: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 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, 176, 177, 181, 182, 185, 187, 188, 193, 194, 199 can be used.

Orange coloring compositions for forming orange filter segments include, for example, C.I. Orange pigments such as Pigment orange 36, 43, 51, 55, 59 and 61 may be used.

Green coloring compositions for forming green filter segments include, for example, C.I. Green pigments such as Pigment Green 7, 10, 36 and 37 can be used. A yellow pigment may be used in combination with the green coloring composition.

Blue coloring compositions for forming blue filter segments include, for example, C.I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and 64 can be used. The blue coloring composition includes C.I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Cyan coloring compositions for forming cyan filter segments include, for example, C.I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16 and 81 can be used.

The magenta coloring composition for forming the magenta filter segment includes, for example, C.I. Pigment Violet 1, 19, C.I. Pigment Red 144, 146, 177, 169, 81 and the like can be used. A yellow pigment may be used in combination with the magenta coloring composition.

Examples of the inorganic pigments include barium sulfate, zinc sulfate, lead sulfate, yellow lead, zinc sulfur, red iron oxide (red iron oxide (III)), cadmium red, Metal oxides such as titanium oxide and tetraoxide, metal sulfides, and metal powders. The inorganic pigment is used in combination with an organic pigment in order to ensure good coating properties, sensitivity, developability and the like while balancing the saturation and lightness.

The coloring composition of the present invention may contain a dye within a range that does not lower the heat resistance for coloring.

Examples of the organic solvent included in the coloring composition of the present invention include organic solvents such as 2-heptanone, 4-heptanone, cyclohexanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, methyl isobutyl ketone, n -Butyl alcohol, 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 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, 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, Ethylene 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 mono Methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, gamma -butyrolactone, methyl ethyl ketone, methyl ethyl ketone, Butylolactone, N, N-dimethylacetoamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m- Dichlorobenzene, m-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, methylcyclohexanol and the like. These may be used alone or in combination of two 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, based on 100 parts by weight of the coloring composition in the coloring composition.

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

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- , Acetophenone-based photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether Benzoin-based photopolymerization initiators such as benzoin ethyl ether, benzoin isopropyl ether and benzyldimethyl ketal, benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone-based photopolymerization initiators such as 4'-methyldiphenyl sulfide, 4'-methyldiphenyl sulfide and the like, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, , 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) - (trichloromethyl) - s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) - (trichloromethyl) -6-styryl-s-triazine, 2- ((trichloromethyl) Naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy- (4'-methoxystyryl) -6-triazine such as 2,4-trichloromethyl- (piperonyl) -6-triazine and 2,4-trichloromethyl Based photopolymerization initiator, a borate-based photopolymerization initiator, a carbazole-based photopolymerization initiator, and an imidazole-based photopolymerization initiator. 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 composition in the coloring composition.

The photopolymerization initiator may be used alone or in admixture of two or more. The photopolymerization initiator may be used alone or in admixture of two or more. Examples of the sensitizer include? -Acyloxime esters, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-diethylaminobenzophenone Compounds may be used in combination. 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 coloring composition.

The coloring composition of the present invention may contain one or two or more coloring agents together with the polymerizable monomer and the photopolymerization initiator in the photocurable transparent resin and the organic solvent in the form of a three-roll mill, a two roll mill, a sand mill, Can be produced by finely dispersing using a dispersing means. The coloring composition containing two or more kinds of coloring agents may be prepared by mixing the respective coloring materials separately finely dispersed in the photocurable transparent resin and the organic solvent. When dispersing the pigment as a coloring agent in the photocurable transparent resin and the organic solvent, a dispersing aid such as a resin type pigment dispersing agent, a surfactant, a pigment derivative and the like may be appropriately contained. The dispersing aid is excellent in the dispersion of the pigment and has an effect of preventing the re-aggregation of the pigment after dispersion. Therefore, when a coloring composition comprising the pigment dispersed in the photo-curable transparent resin and the organic solvent is used by using the dispersing aid A color filter excellent in transparency can be obtained.

As the resinous pigment dispersant, a pigment affinity site having a property of adsorbing to a pigment and a site compatible with the pigment carrier are adsorbed on the pigment to stabilize the dispersion of the pigment on the pigment carrier. 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, Amide or the like formed by the reaction of an alkylamine salt, an alkylamine salt, a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester or a modification thereof, a poly (lower alkyleneimine) (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and the like, Polymer compound, polyester type, modified polyacrylate type, ethylene oxide / propylene oxide addition compound, phosphoric acid ester It is used and the like, which may be used either individually or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, laurylsulfate monoethanolamine, Anionic surfactants such as amine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Alkyl betaine such as alkyldimethylaminoacetic acid betaine, and alkyl imidazoline. These surfactants may be used alone or in admixture of two or more.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment includes a pale yellow aromatic polycyclic compound such as a naphthalene-based or anthraquinone-based pigment which is not generally called a pigment. Examples of the pigment derivative include those disclosed in Japanese Patent Application Laid-Open Nos. 63-305173, 57-15620, 59-40172, 63-17102, 5-9469 May be used alone or in admixture of two or more kinds.

The dispersion 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 coloring agent.

The coloring composition of the present invention may contain a non-photosensitive transparent resin in order to control the solubility and resistance to the developer. The non-photosensitive transparent resin is preferably a transparent resin having a transmittance of 80% or more, more preferably 95% or more in a wavelength region of 400 to 700 nm in a visible light region having no ethylenically unsaturated double bond. Such non-photosensitive transparent resin includes a thermoplastic resin and a thermosetting resin, and they may be used alone or in combination of two or more.

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, polyvinyl acetate, polyurethane resin, An acrylic resin, an alkyd resin, a styrene resin, a polyamide resin, a rubber resin, a cyclic rubber resin, a cellulose, a polybutadiene, and a polyimide resin. Examples of the non-photosensitive thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic 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, based on 100 parts by weight of the coloring agent.

In addition, the coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include hydroquinone, methylhydroquinone, 2,5-di-tert-butylhydroquinone, tert-butylhydroquinone, tert-butyl-beta-benzoquinone, Hydroquinone compounds such as diphenyl-p-benzoquinone, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, tributylphosphine, trioctylphosphine , Tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; triphenylphosphite, trisnonylphenylphosphine, Phosphite compounds such as phosphite, and t-butyl pyrocatechol. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the coloring composition in the coloring composition.

It is also possible to add an adhesion improving agent such as a silane coupling agent in order to improve adhesion with the substrate.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as? -Methacryloxypropyltrimethoxysilane ,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane, Silane, epoxy silanes such as? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and? -Glycidoxypropyltriethoxysilane, N-β Aminoethyl)? -Aminopropyltrimethoxysilane, N-? (Aminoethyl)? -Aminopropyltriethoxysilane, N-? (Aminoethyl)? -Aminopropylmethyldiethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltriethoxysilane And thiosilanes such as? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane, and the like. 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 coloring composition in the coloring composition for a color filter.

The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 占 퐉 or larger, preferably coarse particles of 1 占 퐉 or larger, more preferably coarse particles of 0.5 占 퐉 or larger and mixed dust by means of a centrifugal separation, sintering filter or membrane filter Do.

In order to obtain a uniform coating film, the coloring composition of the present invention is preferably adjusted to have a viscosity of 10 mPa s or less at 25 캜 using an E-type viscometer at a rotation number of 20 rpm in order to obtain a uniform coating film. S or more and 8 mPa · s or less.

The coloring composition of the present invention can be prepared in the form of a solvent-developing type or an alkali development type coloring resist material.

Next, a color filter having filter segments formed from the coloring composition of the present invention will be described.

The color filter is formed with filter segments of at least two colors selected from R (red), G (green), B (blue), Y (yellow), M (magenta) . The filter segments of each color can be formed by using the coloring composition of the present invention by photolithography.

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

As the reflective substrate, it is possible to use a substrate formed of silicon or an aluminum, silver, silver / copper / palladium alloy thin film formed on the transparent substrate.

When each color filter segment is formed by photolithography, the coloring composition prepared as the solvent-developed or alkali-developed coloring resist is dried on a substrate by a coating method such as a spray coat, a spin coat, a slit coat, And the coating thickness is 0.2 to 5 占 퐉. If necessary, the dried film is passed through a mask having a predetermined pattern provided in contact with or in contact with the film, and ultraviolet exposure is performed. After that, a desired pattern is formed by dipping in a solvent or an alkaline developing solution, or spraying the developing solution by spraying or the like to remove un-hardened portions, and then the same operation can be repeated for different colors to produce a color filter. Heating may also be carried out if necessary in order to accelerate the polymerization of the colored resist. According to the photolithography method, a color filter having higher precision than the printing method can be produced.

As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid film formation) development method, and the like can be applied.

Further, in order to increase ultraviolet exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen , And ultraviolet ray exposure may be performed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of the present invention at all. In the examples, &quot; parts &quot; and &quot; parts &quot;

(Synthesis Example 1)

560 parts of cyclohexanone was placed in a reaction vessel, and heated to 80 DEG C while introducing nitrogen gas into the vessel, and at the same temperature, 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 45.0 parts of n-butyl methacrylate, 47.0 parts of methacrylate and 4.0 parts of 2,2'-azobisisobutylonitrile was added dropwise over 1 hour to carry out a polymerization reaction.

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

Next, to 338 parts of the obtained copolymer solution, a mixture of 32.0 parts of 2-methacylethyl isocyanate, 0.4 parts of dibutyltin laurate and 120.0 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours.

After cooling to room temperature, about 2 g of the obtained photo-curable transparent resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. Based on the measured value, the photo-curable transparent resin solution synthesized in the above- Cyclohexanone was added so as to have a weight%, whereby a photocurable transparent resin solution A was prepared. The photocurable transparent resin thus 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 added to the reaction vessel, and the mixture was heated to 80 DEG C while introducing nitrogen gas into the vessel, and 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 over 1 hour to carry out a polymerization reaction.

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

Then, to 220 parts of the obtained copolymer solution, a mixture of 56.0 parts of 2-methacylethyl isocyanate, 0.4 parts of dibutyltin laurate and 220.0 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours.

After cooling to room temperature, cyclohexanone was added so as to have a nonvolatile content of 20% by weight in the same manner as in Synthesis Example 1 to prepare a photo-curable transparent resin solution B. The obtained photocurable transparent resin 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 added to the reaction vessel, and the mixture was heated to 80 DEG C while introducing nitrogen gas into the vessel, and 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate, A mixture of 48.0 parts of acrylate, 15.0 parts of glycerol monomethacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour to carry out 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 azobisisobutylonitrile was dissolved in 80 parts of cyclohexanone. The reaction was further continued at 80 ° C for 1 hour to obtain a copolymer solution .

Next, to 445 parts of the obtained copolymer solution, a mixture of 14.0 parts of 2-methacylethyl isocyanate, 0.4 parts of dibutyl tin dilaurate and 55.0 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours.

After cooling to room temperature, cyclohexanone was added so as to have a nonvolatile content of 20% by weight in the same manner as in Synthesis Example 1 to prepare a photo-curable transparent resin solution C. The obtained photocurable transparent resin 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 compositions was uniformly stirred and then dispersed in glass beads having a diameter of 1 mm for 5 hours using a sand mill, followed by filtration through a filter of 5 m to prepare a copper phthalocyanine dispersion.

Composition of the mixture (copper phthalocyanine dispersion):

? type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 12.00 parts

(Heliogen Blue L-6700F made by BASF)

Dispersant ("Sol Spurs 20000" manufactured by Nihon Lubrizol Corporation) 2.40 parts

Photo-curable transparent resin solution A obtained in Synthesis Example 1 28.10 parts

Cyclohexanone 57.50 parts

Then, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 mu m to obtain a colored composition adjusted as a blue resist material. Table 2 shows the composition of the coloring composition (the weight ratio of the total amount of the coloring composition to 100).

Composition of mixture (coloring composition):

Copper phthalocyanine dispersion 45.05 parts

18.05 parts of the photocurable transparent resin solution A obtained in Synthesis Example 1

Caprylolactone-modified trimethylolpropane triacrylate 4.80 parts

Photopolymerization initiator 2.50 parts

("Irgacure 907" manufactured by Chiba Specialty Chemicals Co., Ltd.)

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.20 part

Leveling agent 0.01 part

(BYK-323 made by Big Chemie Japan)

Cyclohexanone 29.40 part

(Examples 2 to 9 and Comparative Examples 1 to 7)

Each pigment dispersion was obtained in the same manner as in Example 1 except that the composition of the pigment, the dispersant, the photo-curable transparent resin solution and the solvent were changed to the ratios shown in Table 2 (the weight ratio of the total pigment dispersion to 100).

Subsequently, the composition of the pigment dispersion, the photo-curable transparent resin solution, the polymerizable monomer, the photopolymerization initiator, the sensitizer, the organic solvent and the leveling agent was changed to the ratios shown in Tables 3a and 3b (the total weight of the colored composition was 100 parts by weight) , A coloring composition adjusted as each color resist material was obtained in the same manner as in Example 1.

In Table 2,

PB 15: 6 = ε type copper phthalocyanine pigment (CI Pigment Blue 15: 6) ("Helogen Blue L-6700F" manufactured by BASF);

PR 254 = diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Ikega Red B-CF" manufactured by Chiba Specialty Chemicals Co., Ltd.);

PR 177 = anthraquinone-based pigment (CI Pigment Red 177) ("Chromophthalide A2B" manufactured by Chiba Specialty Chemicals);

PY 199 = anthraquinone-based pigment (CI Pigment Yellow 199) ("Cromofta Yellow GT-AD" manufactured by Chiba Specialty Chemicals);

PG 36 = copper phthalocyanine halide pigment (CI Pigment Green 36) ("Lionol Green 6YK" manufactured by Toyo Ink Seiyaku Co., Ltd.);

PY 150 = monoazo pigment (CI Pigment Yellow 150) ("First Village Yellow Yellow Y-5688" manufactured by LANXESS);

Dispersant = "Sol Spurs 20000" manufactured by Nippon Rubriol Corporation;

Resin A = Photo-curable transparent resin solution A obtained in Synthesis Example 1;

Resin B: Photo-curable transparent resin solution B obtained in Synthesis Example 2;

Resin C = Photo-curable transparent resin solution C obtained in Synthesis Example 3

In Tables 3a and 3b,

Monomer A = caprolactone-modified trimethylolpropane triacrylate ("Ebecryl 2047" manufactured by Daicel-Cytech, 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 = trimethylolpropane triacrylate ("NK Ester A-TMPT", Shin-Nakamura Chemical Co., Ltd., solubility parameter: 10.5, double bond equivalent: 99);

Resin A = Photo-curable transparent resin solution A obtained in Synthesis Example 1;

Resin B: Photo-curable transparent resin solution B obtained in Synthesis Example 2;

Resin C = Photo-curable transparent resin solution C obtained in Synthesis Example 3;

Photopolymerization initiator = "IGACURE 907" manufactured by Chiba Specialty Chemicals Co., Ltd.;

&Quot; EAB-F &quot; made by Hodogaya Kagaku Kogyo Co., Ltd.;

Leveling agent = BYK-323 made by Big Chem Japan.

Each color resist material obtained in Examples 1 to 9 and Comparative Examples 1 to 7 was coated on a glass substrate of 100 mm x 100 mm and 0.7 mm thick by using a spin coater to form a coating film having a thickness of 2.0 m. Next, after pre-baking at 70 DEG C for 20 minutes, ultraviolet ray exposure was performed at 100 mJ / cm &lt; ² &gt;. The spectral transmittance of the resulting photocured film was measured using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Kogaku Co., Ltd.), and then immersed in a 0.25% aqueous solution of sodium hydroxide. After immersing for 2 minutes, the spectral transmittance was again measured using a brown rice spectrophotometer, and a color difference (ΔEab) was calculated. The development unevenness was observed using an optical microscope after four minutes of immersion in a 0.25% sodium hydroxide aqueous solution for 2 minutes, and the development unevenness was observed in four steps (?: No development unevenness observed,?: Slight but pale development unevenness, X: streaky, and overall uneven staining). The results are shown in Table 4.

Compared to the cured coating films formed using the color compositions obtained in Comparative Examples 1 to 7, the cured coating film formed using the coloring compositions obtained in Examples 1 to 6 had a color difference (ΔEab) before and after the immersion of the sodium hydroxide aqueous solution was small, Which is a good result.

The cured coating films prepared using the color compositions obtained in Examples 7 to 9 had a color difference (ΔEab) larger than that of the most favorable Example 9 at a blending amount close to the preferable range, Some observations were made.

As described above, since the coloring composition of the present invention is sufficiently cured by ultraviolet irradiation, the 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 color difference of the filter segments of the color filter is eliminated, and a good liquid crystal display device is obtained. Stable obtaining of a good liquid crystal display device is an excellent effect for coping with the liquid crystal display device market in which demand is continuously increasing due to rapid growth due to cost reduction and improvement in throughput due to a decrease in the defective rate of the production line.

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, wherein the polymerizable monomer has a double bond equivalent (M _DC ) the ratio of the solubility parameter (M _SP) ratio (M _SP / M _DC) that is less than 0.10, the solubility parameter (P _SP) of the transparent resin to the double bond equivalent weight (P _DC) of the transparent resin of the (P _SP / P _DC ) of 0.012 or more, the polymerizable monomer is contained in an amount of 30 to 150% of the weight of the transparent resin, Wherein the polymerizable monomer contains at least one of caprolactone-modified trimethylolpropane triacrylate or ethylene oxide-modified trimethylolpropane triacrylate. The coloring composition according to claim 1, wherein the polymerizable monomer has a double bond equivalent (M _DC ) of 120 to 350. The coloring composition according to claim 1, wherein the double bond equivalent (P _DC ) of the transparent resin is from 200 to 800. A color filter comprising a filter segment formed from the coloring composition of any one of claims 1 to 3 on a substrate.