JP2009025634A - Colored composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition having high UV curability and a color filter with filter segments free of a color difference due to faulty curing. <P>SOLUTION: The colored composition contains a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a pigment and an organic solvent, wherein the ratio of the solubility parameter M<SB>SP</SB>of the polymerizable monomer to the double bond equivalent M<SB>DC</SB>of the polymerizable monomer, M<SB>SP</SB>/M<SB>DC</SB>is ≤0.10, the ratio of the solubility parameter P<SB>SP</SB>of the transparent resin to the double bond equivalent P<SB>DC</SB>of the transparent resin, P<SB>SP</SB>/P<SB>DC</SB>is ≥0.012, and the weight of the polymerizable monomer is 30-150% of the weight of the transparent resin. The color filter has filter segments formed using the colored composition on a substrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a coloring composition and a color filter which are preferably used for producing a color filter constituting a color liquid crystal display device, a color image pickup tube element and the like.

  In recent years, liquid crystal display devices have been applied to TV monitor applications, personal computer monitor applications, mobile applications, and the like. For color filters used in liquid crystal display devices, the required level of lightness, color purity, etc. has been increasing in order to improve color reproducibility. In addition, since the liquid crystal display device is used for a long time, there is a strong demand for quality regarding color filters, such as heat resistance and light resistance. Furthermore, the required levels of coating uniformity, sensitivity, developability, and pattern shape when forming each color filter segment are also increasing for colored compositions used in the production of color filters. In order to meet these requirements, the concentration of coloring components such as pigments in the colored composition is increased, and the concentration of components of the photocurable resin and the monomer is decreased.

  In order to meet the ever-increasing demand for liquid crystal display devices, the production time of color filters has been shortened by simplifying the process.

  However, increasing the pigment component of the colored composition to reduce the photocuring component, or shortening the UV irradiation time to simplify the color filter manufacturing process, results in poor photocuring of the colored coating film. Specifically, a poorly cured coating film refers to a colored coating film in which a sufficiently cured portion and a portion that is not sufficiently cured are mixed in a portion to be cured. By developing the poorly cured coating film with an alkali, a color difference is produced between a sufficiently cured portion and a portion that is not sufficiently cured.

  An attempt was made to solve the above-described problem of color difference using the prior art.

  First, using a photosensitive coloring composition containing a high-sensitivity photopolymerization initiator disclosed in Patent Document 1, whether or not the coating curing failure can be solved even with a small amount of photocuring component and a small amount of UV irradiation did. However, even when using a highly sensitive photopolymerization initiator and increasing its content, the amount of the photocuring component to be cured is limited so that it becomes cured and saturated, and there is no color difference due to poor curing. I didn't.

Next, the A component consisting of a polyfunctional (meth) acrylic monomer, the B component consisting of a polymer having a structural unit containing a specific cyclic hydrocarbon, and the C component consisting of a monofunctional monomer, disclosed in Patent Document 2. And an alkali-resistant photosensitive composition containing a specific proportion of the D component comprising at least one of a photopolymerization initiator and a photosensitizer. However, since the B component made of a polymer contained in the photosensitive composition is not cured by ultraviolet irradiation, the coating film peeled off by alkali development, and on the contrary, a large color difference was caused.
Japanese Patent Laid-Open No. 2005-099488 JP 2002-318453 A

  Therefore, an object of the present invention is to provide a coloring composition having high curability by ultraviolet rays and a color filter having a filter segment in which no color difference due to poor curing is observed.

The colored composition of the present invention is a colored composition containing a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a dye and an organic solvent, wherein the polymerizable 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 monomer is 0.10 or less, and the transparent resin with respect to the double bond equivalent P _DC of the transparent resin The ratio P _SP / P _DC of the solubility parameter P _SP is 0.012 or more, and the weight of the polymerizable monomer is 30 to 150% of the weight of the transparent resin.

  Moreover, the color filter of this invention comprises the filter segment formed using the coloring composition of this invention on a board | substrate.

  Since the colored composition of the present invention is sufficiently cured by irradiation with ultraviolet rays, the cured coating film formed using the colored composition of the present invention exhibits sufficient resistance to an alkaline developer. Thereby, the in-plane color difference of the filter segment which a color filter comprises is eliminated, and a favorable liquid crystal display device is obtained. The stable acquisition of a good liquid crystal display device is an excellent effect to respond to the liquid crystal display device market, which is increasing in demand due to rapid growth due to cost reduction and throughput improvement due to a decrease in defective rate of production line It is.

  First, the coloring composition of this invention is demonstrated concretely.

  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 dye, and an organic solvent.

In the colored 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, and the transparent 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 resin is 0.012 or more, and the weight of the polymerizable monomer is 30 to 30% of the weight of the transparent resin. 150%.

The solubility parameter M _SP of the polymerizable monomer in the present invention is “Polymer Eng. & Sci.” Vol. 14, No. 2 (1974), p. 148-P. It is calculated by the Fedors equation described in 154, that is, the following equation (1).

Formula (1) M _SP = (ΣΔe _i / ΣΔv _i ) ^1/2
(Δe _i is the evaporation energy at 25 ° C. belonging to atoms or groups, and Δv _i is the molar volume at 25 ° C.)
Δe _i and Δv _i in the above formula are constant numerical values given to i atoms and groups in the molecule. Table 1 shows representative examples of Δe and Δv values given for atoms or groups.

  For example, the solubility parameter of 2-hydroxyethyl acrylate represented by the following structural formula (2) is calculated using these formulas.

  Formula (2)

2-hydroxyethyl acrylate contains 1 ═CH ₂ , 1 —CH═, 1 —COO—, ₂ —CH ₂ — and 1 —OH (C adjacent). _i is 1030 + 1030 + 4300 + 1180 × 2 + 5220 = 13940 (cal / mol). Also, 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 ).

When two or more kinds of polymerizable monomers are mixed and used, the solubility parameter value of the mixed polymerizable monomer calculated from the following formula is used as the solubility parameter of the polymerizable monomer.

M _SPmix = a _M1 M _SPM1 + a _M2 M _SPM2 + a _M3 M _SPM3 + ... + a _Mn M _SPMn
M _SPmix : Solubility parameter of mixed polymerizable monomer
M _SPM1 : Solubility parameter of polymerizable monomer 1
M _SPM2 : Solubility parameter of polymerizable monomer 2
M _SPM3 : Solubility parameter of polymerizable monomer 3
・
・
M _SPMn : Solubility parameter of polymerizable monomer n a _M1 : Weight fraction of polymerizable monomer 1 in mixed polymerizable monomer a _M2 : Weight fraction of polymerizable monomer 2 in mixed polymerizable monomer a _M3 : Mixed polymerizable Weight fraction of polymerizable monomer 3 in monomer
・
・
a _Mn : Weight fraction of the polymerizable monomer n in the mixed polymerizable monomer The double bond equivalent of the polymerizable monomer is defined by the following formula and represents the amount of double bonds contained in one molecule of the polymerizable monomer. It becomes a scale. If the compounds have the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases.

(Double bond equivalent) = (molecular weight of polymerizable monomer) / (number of double bonds in one molecule of polymerizable monomer)
When two or more kinds of polymerizable monomers are mixed and used, the double bond equivalent value of the mixed polymerizable monomer calculated from the following formula is defined as the double bond equivalent of the polymerizable monomer.

M _DCmix = a _M1 M _DCM1 + a _M2 M _DCM2 + a _M3 M _DCM3 + ... + a _Mn M _DCMn
M _DCmix : Double bond equivalent of mixed polymerizable monomer
M _DCM1 : Double bond equivalent of polymerizable monomer 1
M _DCM2 : Double bond equivalent of polymerizable monomer 2
M _DCM3 : Double bond equivalent of polymerizable monomer 3
・
・
M _DCMn : Double bond equivalent of polymerizable monomer n a _M1 : Weight fraction of polymerizable monomer 1 in mixed polymerizable monomer a _M2 : Weight fraction of polymerizable monomer 2 in mixed polymerizable monomer a _M3 : Mixing Weight fraction of polymerizable monomer 3 in polymerizable monomer
・
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a _Mn : Weight fraction of the polymerizable monomer n in the mixed polymerizable monomer 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 0.1 When it becomes larger, curing of the coating film surface proceeds by ultraviolet irradiation, and cracks and the like are generated in the cured coating film. M _SP / M _DC is preferably 0.03 or more, and 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 120 to 350, and more preferably 150 to 300. When the double bond equivalent of the polymerizable monomer is smaller than 120, curing of the coating film surface may progress due to ultraviolet irradiation, and cracks may occur in the cured coating film. Moreover, when the double bond equivalent of a polymerizable monomer is larger than 350, the sensitivity of a coloring composition is not enough, and even if it irradiates with an ultraviolet-ray, a coating film may not harden | cure.

  As the polymerizable monomer, 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), tricyclodecanyl Acrylate (SP: 11.6, DC: 84), tricyclodecanyl methacrylate (SP: 11.0, DC: 98), melamine acrylate (SP: 11.3, DC: 149), melamine methacrylate (SP : 10.9, DC: 163), epoxy acrylate (SP: 8) 7, DC: 295), various acrylic esters and methacrylic esters such as epoxy methacrylate (SP: 8.6, DC: 309), 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-hydroxymethyl acrylamide (SP: 15.4, DC: 101), N-hydroxymethyl methacrylamide (SP: 14.5, DC: 115) , Acrylonitrile (SP: 11.1, DC: 53) and the like. Those in which a part of the carbon chain of the polymerizable monomer is modified with caprolactone, ethylene oxide, or propylene oxide can also be used.

  A polymeric monomer can be used individually by 1 type or in mixture of 2 or more types.

  The transparent resin having an ethylenically unsaturated double bond in the present invention (hereinafter referred to as a photocurable transparent resin) has an ethylenically unsaturated double bond and transmits in the entire wavelength region of 400 to 700 nm in the visible light region. The resin is preferably 80% or more, more preferably 95% or more. The solubility parameter of the photo-curable transparent resin is calculated by the Fedors equation in the same manner as the polymerizable monomer. In the case of a photocurable transparent resin, it is calculated from the theoretical monomer composition (molar ratio) constituting the resin shown in the following formula.

Solubility parameter P _SP of photo-curing transparent resin = Wta × SPa + Wtb × SPb + Wtc × SPc
Wta: mole fraction of monomer A Wtb: mole fraction of monomer B Wtc: mole fraction of monomer C
・
・
SPa: solubility parameter of monomer A SPb: solubility parameter of monomer B SPc: solubility parameter of monomer B
・
・
For example, when the constituent monomers of the photocurable transparent resin are 70% by weight of methacrylic acid (molecular weight: 86, solubility parameter: 10.7) and 30% by weight of methyl methacrylate (molecular weight: 100, solubility parameter: 9.3) The solubility parameter of the resin is: (methacrylic acid mole fraction) × (methacrylic acid solubility parameter) + (methyl methacrylate mole fraction) × (methyl methacrylate solubility parameter) = (70/86) / (70/86 + 30 /100)×10.7+(30/100)/(70/86+30/100)×9.3=10.32.

  Moreover, when mixing and using 2 or more types of photocurable transparent resins, let the solubility parameter value of the mixed photocurable transparent resin calculated from a following formula be a solubility parameter of photocurable transparent resin.

P _SPmix = a _P1 M _SPM1 + a _P2 M _SPM2 + a _P3 M _SPM3 + ... + a _Pn M _SPMn
P _SPmix : Solubility parameter of mixed photo-curing transparent resin
P _SPS1 : Solubility parameter of photo-curable transparent resin 1
P _SPS2 : Solubility parameter of photo-curable transparent resin 2
P _SPS3 : Solubility parameter of photo-curable transparent resin 3
・
・
M _SPSn : Solubility parameter of photocurable transparent resin n a _P1 : Weight fraction of photocurable transparent resin 1 in mixed photocurable transparent resin a _P2 : Photocurable transparent resin 2 in mixed photocurable transparent resin Weight fraction a _P3 : weight fraction of the photocurable transparent resin 3 in the mixed photocurable transparent resin
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・
a _Pn : Weight fraction of the photocurable transparent resin n in the mixed photocurable transparent resin The double bond equivalent of the photocurable transparent resin is defined by the following formula and is a double bond contained in the molecule. It is a measure of quantity. In the case of a photocurable transparent resin having the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases.

(Double bond equivalent) = (weight average molecular weight of photocurable transparent resin) / (number of double bonds in one molecule of photocurable transparent resin)
When mixing and using two or more types of photocurable transparent resins, the value of the mixed photocurable transparent resin calculated from the following formula is the double bond equivalent of the photocurable transparent resin.

_{P DCmix = a P1 P DCP1 +} a P2 P DCP2 + a P3 P DCP3 + ··· + a Pn P DCPn
P _DCmix : Double bond equivalent of mixed photo-curing transparent resin
P _DCP1 : Double bond equivalent of photo-curable transparent resin 1
P _DCP2 : Double bond equivalent of the photocurable transparent resin 2
P _DCP3 : Double bond equivalent of the photocurable transparent resin 3
・
・
P _DCPn : Double bond equivalent of photocurable transparent resin n a _P1 : Weight fraction of photocurable transparent resin 1 in mixed photocurable transparent resin a _P2 : Photocurable transparent in mixed photocurable transparent resin Weight fraction of resin 2 a _P3 : Weight fraction of photocurable transparent resin 3 in mixed photocurable transparent resin
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a _Pn : Weight fraction of the photocurable transparent resin n in the mixed photocurable transparent resin Ratio P of the solubility parameter _PSP of the photocurable transparent resin to the double bond equivalent _PDC of the photocurable transparent resin when _{the SP} / P _DC is 0.012 or less, it reduces the photocurable colored composition, a coating film is not sufficiently cured even when ultraviolet irradiation. P _SP / P _DC is preferably 0.05 or less, and 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 200 to 800, more preferably 300 to 700. When the double bond equivalent of the photocurable transparent resin is smaller than 200, curing of the coating film surface may proceed due to ultraviolet irradiation, and cracks may occur in the cured coating film. Moreover, when the double bond equivalent of photocurable transparent resin is larger than 800, sufficient sensitivity of a coloring composition cannot be obtained, and even if it irradiates with an ultraviolet-ray, a coating film will not fully harden | cure.

  As a photocurable transparent resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting with cinnamic acid. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  A photocurable transparent resin can be used individually by 1 type or in mixture of 2 or more types.

  In the colored composition of the present invention, the weight of the polymerizable monomer is 30 to 150%, preferably 50 to 100%, of the weight of the photocurable transparent resin. In the colored composition of the present invention, the polymerizable monomer serves as a main curing agent, and the photocurable transparent resin serves as a curing aid. The photocurable transparent resin itself has a smaller influence on photocuring compared to the polymerizable monomer, while the polymerizable monomer is defined as described above because the product is cured by light. Both are preferably included in a well-balanced manner.

  When the coating film formed using the colored composition of the present invention is irradiated with ultraviolet rays, the polymerization of the polymerizable monomer is promoted from the ethylenically unsaturated double bond of the photocurable transparent resin, and the ultraviolet rays are irradiated. The entire coating film at the portion thus cured is sufficiently cured without causing poor curing. When the weight of the polymerizable monomer exceeds 150% of the weight of the photocurable transparent resin, there is little photocurable transparent resin as a starting point for polymerization of the polymerizable monomer, and the polymerizable monomer is not sufficiently cured. It is not preferable. On the other hand, if it is less than 30%, the polymerizable monomer is sufficiently cured, but the absolute amount of the polymerizable monomer is reduced, and the coating film is not sufficiently cured, which is not preferable.

  As the dye contained in the colored composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.

  Below, the specific example of the organic pigment which can be preferably used for the coloring composition of this invention is shown by a color index number.

  Red pigmented compositions for forming red filter segments include, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2. 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 1
7, 18, 20, 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, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 19 It can be used yellow pigment 199, and the like.

  For example, orange pigments such as C.I. Pigment orange 36, 43, 51, 55, 59, 61 can be used for the orange coloring composition for forming the orange filter segment.

  For the green coloring composition for forming the green filter segment, green pigments such as C.I. Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.

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

  For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.

  As the magenta color coloring composition for forming the magenta color filter segment, purple pigments and red pigments such as C.I. Pigment Violet 1, 19, C.I. Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.

  Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. And metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

Examples of the organic solvent contained in the colored composition of the present invention include 2-heptanone, 4-heptanone, cyclohexanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-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 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, diisobutyl ketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol Monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 3-methoxy Butyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, N, N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, o-dichlorobenzene M-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, Le cyclohexanol, and the like. These may be used alone or in admixture of two or more. The organic solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

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

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. . A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  The coloring composition of the present invention comprises one or two or more dyes, together with the polymerizable monomer and the photopolymerization initiator, in the photocurable transparent resin and the organic solvent, a three roll mill, a two roll mill, a sand mill, It can be produced by finely dispersing using various dispersing means such as a kneader and an attritor. Moreover, the coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what disperse | distributed each pigment | dye separately in the said photocurable transparent resin and the organic solvent separately. When the pigment is dispersed in the photocurable transparent resin and the organic solvent as a coloring matter, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the dispersion aid is used to disperse the pigment in the photocurable transparent resin and the organic solvent. When the composition is used, a color filter having excellent transparency can be obtained.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can 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 also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

The coloring composition of the present invention can contain a non-photosensitive transparent resin in order to control solubility and resistance to a developer. The non-photosensitive transparent resin is a transparent resin that does not have an ethylenically unsaturated double bond and has a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. . Such a non-photosensitive transparent resin includes a thermoplastic resin and a thermosetting resin, and these can be used alone or in admixture 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, and polyurethane resin. , Polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyimide resins, and the like. Examples of the non-photosensitive thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include hydroquinone, methyl hydroquinone, 2,5 di-tert-butyl hydroquinone, tert-butyl hydroquinone, tert-butyl-β-benzoquinone, tert-butyl hydroquinone, 2,5-diphenyl-p-benzoquinone, etc. Hydroquinone compounds, 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, tribenzylphosphine Phosphine compounds such as trioctylphosphine oxide, phosphine oxide compounds such as triphenylphosphine oxide, triphenyl phosphite, tris Examples thereof include phosphite compounds such as nonylphenyl phosphite and t-butylpyrocatechol. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the dye in the coloring composition.

  Moreover, in order to improve adhesiveness with a board | substrate, adhesion improvement agents, such as a silane coupling agent, can also be contained.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the dye in the color filter coloring composition.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Further, the colored composition of the present invention has a viscosity of 10 mPa · s or less measured at 25 ° C. using an E-type viscometer at a rotation speed of 20 rpm in order to obtain a uniform coating without causing coating unevenness. It is preferable to adjust so that it may become, and it is more preferable to adjust so that it may become 1 mPa * s or more and 8 mPa * s or less.

  The coloring composition can be prepared in the form of a solvent development type or alkali development type colored resist material.

  Below, the color filter which comprises the filter segment formed using the coloring composition of this invention is demonstrated.

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

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

  As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  When forming each color filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating or the like is applied on the substrate with the coloring composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV 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 that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.
(Synthesis Example 1)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting 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 Then, a mixture of 47.0 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, then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution was obtained.

  Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 120.0 parts of cyclohexanone was added to 338 parts of the obtained copolymer solution at 70 ° C. for 3 hours. It was dripped over.

After cooling to room temperature, about 2 g of the obtained photocurable transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-volatile content was found in the previously synthesized photo-curable transparent resin solution. Cyclohexanone was added so that it might become 20 weight%, and the photocurable transparent resin solution A was prepared. The obtained photocurable transparent resin had a weight average molecular weight of 20000, a double bond equivalent of 470, and a solubility parameter of 11.0.
(Synthesis Example 2)
520 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 63.0 of 2-hydroxyethyl methacrylate A mixture of 66.0 parts of glycerol monomethacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction.

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

  Next, with respect to 220 parts of the obtained copolymer solution, a mixture of 56.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 220.0 parts of cyclohexanone was added at 70 ° C. for 3 hours. It was dripped over.

After cooling to room temperature, cyclohexanone was added in the same manner as in Synthesis Example 1 so that the nonvolatile content was 20% by weight to prepare a photocurable transparent resin solution B. The obtained photocurable transparent resin had a weight average molecular weight of 20000, a double bond equivalent of 270, and a solubility parameter of 11.0.
(Synthesis Example 3)
480 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 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 benzyl methacrylate, 15.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction.

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

  Next, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 55.0 parts of cyclohexanone is added to 445 parts of the obtained copolymer solution at 70 ° C. for 3 hours. It was dripped over.

After cooling to room temperature, cyclohexanone was added in the same manner as in Synthesis Example 1 so that the nonvolatile content was 20% by weight to prepare a photocurable transparent resin solution C. The resulting photocurable transparent resin had a weight average molecular weight of 20000, a double bond equivalent of 1000, and a solubility parameter of 10.8.
[Example 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.

ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 12.00 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Co., Ltd.) 2.40 parts Photocurable transparent resin solution A obtained in Synthesis Example 1 28.10 parts Cyclohexanone 57.50 parts Next, a mixture having the following composition was made uniform. After stirring and mixing as described above, the mixture was filtered through a 1 μm filter to obtain a colored composition prepared as a blue resist material. Table 1 shows the composition of the colored composition (weight ratio where the total amount of the colored composition is 100).

Copper phthalocyanine dispersion 45.05 parts Photocurable transparent resin solution A obtained in Synthesis Example 1 18.05 parts Caprolactone-modified trimethylolpropane triacrylate 4.80 parts Photopolymerization initiator 2.50 parts (Ciba Specialty "Irgacure 907" manufactured by Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.20 parts Leveling agent 0.01 parts ("BYK-323" manufactured by Big Chemie Japan)
Cyclohexanone 29.40 parts [Examples 2-9 and Comparative Examples 1-7]
The composition of the pigment, dispersant, photocurable transparent resin solution, and solvent was changed to the ratio shown in Table 2 (weight ratio with the total amount of the pigment dispersion being 100), and each color pigment dispersion was changed in the same manner as in Example 1. Obtained.

  Subsequently, the ratio of the pigment dispersion, the photocurable transparent resin solution, the polymerizable monomer, the photopolymerization initiator, the sensitizer, the organic solvent, and the leveling agent shown in Table 3 (weight based on the total amount of the colored composition 100) A colored composition prepared as each color resist material was obtained in the same manner as in Example 1 except that the ratio was changed to (Ratio).

PB15: 6: ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
(BASF "Heliogen Blue L-6700F")
PR254: Diketopyrrolopyrrole pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals) PR177: Anthraquinone pigment (CI Pigment Red 177)
(“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals) PY199: Anthraquinone pigment (CI Pigment Yellow 199)
("Chromoval Yellow GT-AD" manufactured by Ciba Specialty Chemicals)
PG36: Copper halide phthalocyanine pigment (CI Pigment Green 36)
("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
PY150: Monoazo pigment (CI Pigment Yellow 150)
("Fanchon First Yellow Y-5688" manufactured by LANXESS)
Dispersant: “Solsperse 20000” manufactured by Nippon Lubrizol
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

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: trimethylolpropane triacrylate (“NK Ester 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” manufactured by Ciba Specialty Chemicals
Sensitizer: "EAB-F" manufactured by Hodogaya Chemical Co., Ltd.
Leveling agent: BYK-323 manufactured by Big Chemie Japan
Each color resist material obtained in Examples 1 to 9 and Comparative Examples 1 to 7 was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater to form a coating film having a thickness of 2.0 μm. Formed. 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 microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and then immersed in a 0.25% aqueous sodium hydroxide solution. After immersion for 2 minutes, the spectral transmittance was measured again using a microspectrophotometer, and the color difference ΔEab was calculated. Further, after immersing in a 0.25% aqueous sodium hydroxide solution for 2 minutes, development spots were observed using an optical microscope, and four stages (◎: no development spots were observed, ○: slight but thin development spots) , Δ: a thin development spot was observed on the whole, and ×: a development spot was observed on the whole. The results are shown in Table 4.

  The cured coating film formed using the colored composition obtained in Examples 1 to 6 was more sodium hydroxide than the cured coating film formed using the colored composition obtained in Comparative Examples 1 to 7. The color difference ΔEab before and after the immersion of the aqueous solution was small, and good results were obtained with no occurrence of development spots.

  Furthermore, the cured coating films produced using the colored compositions obtained in Examples 7 to 9 have a color difference ΔEab larger than that of Example 9 where the blending amount is close to the preferred range, and development stains are also generated. Compared to Example 9, the results are slightly observed.

Claims (4)

A polymerizable composition containing a polymerizable monomer having an ethylenically unsaturated double bond, a transparent resin having an ethylenically unsaturated double bond, a dye and an organic solvent, wherein the double bond equivalent M _{DC of the} polymerizable monomer The ratio M _SP / M _DC of the solubility parameter M _SP of the polymerizable monomer to 0.10 or less, and the ratio P of the solubility parameter P _SP of the transparent resin to the double bond equivalent P _DC of the transparent resin _SP / P _DC is not less 0.012 or more, and the weight of the polymerizable monomer, the coloring composition, wherein said 30 to 150% of the weight of the transparent resin. The coloring composition according to claim 1, wherein the double bond equivalent M _{DC of the} polymerizable monomer is 120 to 350. Claim 1 or 2 coloring composition according double bond equivalent P _DC of the transparent resin is characterized in that 200 to 800.   The color filter which comprises the filter segment formed using the coloring composition of any one of Claims 1 thru | or 3 on a board | substrate.