JP5449883B2 - Coloring composition for color filter, color filter using the same, and liquid crystal display device - Google Patents

Description

  The present invention relates to a green coloring composition for a color filter used for the production of a color filter used for a color liquid crystal display device, a color imaging device, and the like, and a color filter using the same.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The display device performs display, and color display is possible by providing a color filter between two polarizing plates.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is arranged. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to form them at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include contrast ratio and brightness. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, high contrast is indispensable for realizing a high-quality liquid crystal display device.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  In general, in order to achieve high brightness and high contrast of a color filter, it is essential to make a pigment dispersion that is made as close as possible to primary particles by performing finer processing of the pigment. As a result, light scattering by the pigment can be suppressed, and by increasing the transparency of the dispersion, the spectral spectrum of the dispersion can have a high transmittance, so it is possible to create a color filter with high brightness and high contrast. it can.

  Green, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, is a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) as the main pigment. ) Was common. However, as long as copper halide phthalocyanine can be used, it has been difficult to achieve both high contrast ratio and high brightness.

  In order to solve these problems, zinc halide phthalocyanine, which has a vivid color tone and a wide color display area, and has replaced the central metal with zinc from the current copper halide phthalocyanine pigment as a green pigment with high coloring power. Pigments have been used.

  However, the halogenated zinc phthalocyanine green pigment has higher acidity than the halogenated copper phthalocyanine green pigment. Due to the influence of this high acidity, it exhibits higher solubility than other pigment types, so that it is easily dissolved and extracted in the liquid crystal phase laminated on the color filter layer. As a result, the voltage holding ratio is lowered, causing display unevenness, alignment failure, and the like, which is a cause of lowering the performance as a liquid crystal display element. At present, when other pigments are used, the voltage holding ratio is 95% or more, whereas in the case of the halogenated zinc phthalocyanine green pigment, it is only 90% or less, and improvement thereof has been desired. A liquid crystal display device incorporating a color filter with a reduced voltage holding ratio is not preferable because it causes display unevenness on the screen or a so-called image burn-in phenomenon in which the image does not change even when the image is fixed.

  For this reason, improving the voltage holding ratio is a major problem in producing a color filter using a halogenated zinc phthalocyanine green pigment as a green pigment.

JP-A-10-130547 JP 2001-141922 A JP 2007-204658 A

  The present invention has been made under the circumstances as described above, and improves the decrease in voltage holding ratio of a liquid crystal display device, which has been a problem when using a green pigment made of zinc halide phthalocyanine, and exhibits excellent lightness. It aims at providing the green coloring composition for filters, the color filter which comprises it, and the liquid crystal display device which comprises the color filter.

In order to solve the above problems, a first aspect of the present invention includes a green colorant containing a halogenated zinc phthalocyanine pigment, a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin, and active energy ray curing. and sex polymerization initiator, a photosensitive coloring composition containing a solvent, the voltage holding ratio of the liquid crystal display device comprising a color filter obtained by using the photosensitive coloring composition Ri der 90%, the The photopolymerizable monomer includes a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and the number of urethane groups of the polyfunctional urethane acrylate is 0.7 ×. 10 ^-3 mol / g or more, the double bond groups is at 4.5 × ¹⁰ -3 mol / g or more, the photopolymerizable monomer in the solid content of the colored composition Content provides for a color filter photosensitive coloring composition, characterized in der Rukoto 15 wt% or more 56 wt% or less.

  In such a photosensitive color composition for color filters, the content of the zinc halide phthalocyanine pigment can be 20 to 100 parts by weight with respect to 100 parts by weight of the green colorant.

  Alternatively, those containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be used as the photopolymerizable monomer.

  In this case, the content of the photopolymerizable monomer in the solid content of the colored composition can be 10 wt% or more and 25 wt% or less.

  According to a second aspect of the present invention, there is provided a color filter comprising a green pixel formed using the above-mentioned photosensitive coloring composition.

  According to a third aspect of the present invention, there is provided a liquid crystal display device comprising the color filter.

  According to the present invention, it is possible to manufacture a color filter with higher brightness than when copper phthalocyanine is used as a green pigment. In addition, since the green pigment component eluted from the green colored layer into the liquid crystal can be reduced, the decrease in the voltage holding ratio of the liquid crystal display device, which has been a problem when using a zinc halide phthalocyanine green pigment, has been improved. There exists an effect that the photosensitive coloring composition for color filters can be obtained.

  Hereinafter, various embodiments of the present invention will be described.

  A color composition for a color filter according to the first embodiment of the present invention includes a green colorant containing a halogenated zinc phthalocyanine pigment, a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin, and an active energy. Contains a linear curable polymerization initiator and a solvent.

  Hereafter, each structural component of this coloring composition for color filters is demonstrated.

<Green colorant>
One of the characteristics of the photosensitive coloring composition for a color filter according to the first embodiment of the present invention is to use a green colorant containing a halogenated zinc phthalocyanine pigment.

  A typical zinc halide phthalocyanine pigment represented by a color index (CI) number is C.I. I. Pigment Green 58 etc. can be mentioned. By using a halogenated zinc phthalocyanine pigment, it is possible to obtain a high brightness not obtained with other green pigments.

  As the halogenated zinc phthalocyanine pigment, those obtained by a known production method can be used. In particular, when measured using n-hexylamine as a basic substance produced by the method described in Coloring Materials, 67 [9], 547-554 (1994), the amount of acidic functional groups on the pigment surface is: Preferably, 100 μmol / g or more, more preferably 200 μmol / g or more can be used.

  In addition to the zinc halide phthalocyanine pigment, other green pigments and yellow pigments can be used in combination with the green colorant for color adjustment and complementary color purposes.

  Other green pigments that can be used in combination include C.I. I. Pigment Green 7, 10, 36, 37 and the like. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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 And the like can be given 182,185,187,188,193,194,198,199,213,214. Especially, C.I. I. Pigment Yellow 138, 139, 150, and 185 can be preferably used.

  The content of the preferable pigment component in all the non-volatile components of the green coloring composition according to the present embodiment is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the content of the pigment component is less than 10% by weight, it becomes difficult to obtain sufficient color reproducibility, and when it exceeds 90% by weight, the content of the pigment carrier is lowered and the stability of the coloring composition tends to be deteriorated. .

  Preferred pigment ratios are 20-100% by weight of the halogenated zinc phthalocyanine pigment, 0-80% by weight of the halogenated copper phthalocyanine pigment, and 0-50% by weight of the yellow pigment, based on the total weight of the pigment component.

  More preferable pigment ratios are 50 to 90% by weight of the halogenated zinc phthalocyanine pigment, 5 to 45% by weight of the halogenated copper phthalocyanine pigment, and 5 to 45% by weight of the yellow pigment based on the total weight of the pigment component. . The chromaticity region can be expanded by such a composition ratio of the pigment.

  The green coloring composition according to this embodiment using the halogenated zinc phthalocyanine pigment is applied to a glass substrate or the like so as to have the same chromaticity as the green coloring composition using the halogenated copper phthalocyanine pigment, When the transmittance is measured, the transmittance is higher than the coating film of the colored composition using the copper phthalocyanine pigment in the vicinity of about 530 nm from about 450 nm. In particular, the transmittance peak shows a value of about 90%, which is about 5% higher transmittance. Therefore, by combining with a backlight generally used in color liquid crystal display devices, C.I. I. Pigment Green 36 and C.I. I. High brightness that cannot be obtained with a green coloring composition using a halogenated copper phthalocyanine pigment such as CI Pigment Green 7 can be obtained.

  It is preferable that the pigment used for the green coloring composition according to the present embodiment is a product that has been subjected to salt milling and refined. Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes nearly amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution in which the primary particle diameter is very fine and the width of the distribution is wide.

  It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the green pigment contained in the green coloring composition which concerns on this embodiment is the range of 20-100 nm. When the primary particle size is smaller than 20 nm, dispersion in an organic solvent becomes difficult. When the primary particle size is larger than 100 nm, it is difficult to obtain a sufficient contrast ratio. A particularly preferable range is 25 to 85 nm.

  As the water-soluble inorganic salt used in the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight, based on the total weight of the pigment component, in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent used for the salt milling treatment functions to wet the pigment and the water-soluble inorganic salt, and can dissolve (mix) in water and does not substantially dissolve the water-soluble inorganic salt used. There is no particular limitation. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates.

  Specific examples of the water-soluble organic solvent include, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tri Ethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or liquid Polypropylene glycol or the like is used. The water-soluble organic solvent is preferably used in the range of 5 to 1000% by weight, and most preferably in the range of 50 to 500% by weight, based on the total weight of the pigment component.

  When performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and particularly preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment component.

<Dye derivative>
In the coloring composition for a color filter according to this embodiment, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine.

  Among these compounds, organic pigment derivatives represented by the general formula P-Lm are preferable.

  In the general formula P-Lm, P is an organic pigment residue, L is a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group, and m is an integer of 1 to 4.

  Examples of the organic pigment derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. What is described can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the organic pigment derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. When the pigment derivative is less than 1 part by weight relative to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated.

  In the general formula P-Lm, examples of the organic pigment constituting the organic pigment residue of P include the following. For example, diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavan Anthraquinone pigments such as Throne, Antanthrone, Indanthrone, Pyrantron, and Biolantron; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindolinone pigments; Pigments; selenium pigments; and metal complex pigments.

<Photopolymerizable monomer>
The photopolymerizable monomer is a monomer whose polymerization is induced by radicals. As a photopolymerizable monomer that can be used in the photosensitive composition according to this embodiment, a polyfunctional isocyanate is added to a (meth) acrylate having a hydroxyl group. And a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting with acrylate, or an acrylate containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. The combination of the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate is arbitrary and is not particularly limited. Further, one kind of polyfunctional urethane acrylate, or acrylate containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate may be used alone, or two or more kinds may be used in combination.

  Here, as the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol Propane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate , Glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy The reaction product of group-containing compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  The photopolymerizable monomer that can be used in the photosensitive composition according to this embodiment has a hydroxyl group in addition to the polyfunctional urethane acrylate described above or an acrylate containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. When reacting polyfunctional isocyanate with (meth) acrylate, a component having a double bond group that was not obtained as a polyfunctional urethane acrylate having a (meth) acryloyl group may be included as another monomer.

In addition, as for the polyfunctional urethane acrylate mentioned above, it is desirable that the number of urethane groups is 0.7 × 10 ⁻³ mol / g or more and the number of double bond groups is 4.5 × 10 ⁻³ mol / g or more. When the number of urethane groups in the polyfunctional urethane acrylate is less than 0.7 × 10 ⁻³ mol / g, the cured photosensitive composition tends to swell with a chemical or a solvent and is formed on the photosensitive composition layer. The transparent electrode (ITO) is cracked or easily extracted into the liquid crystal phase laminated on the photosensitive composition layer. As a result, the voltage holding ratio is lowered, the occurrence of display unevenness, alignment failure, and the like are caused, the performance as a liquid crystal display element is lowered, and the display quality is greatly lowered. Moreover, when the number of double bond groups is less than 4.5 * 10 < ^-3 > mol / g, since exposure sensitivity falls and resolution deteriorates, it is unpreferable in any case.

<Non-photosensitive resin and / or photosensitive resin>
The photosensitive composition according to this embodiment is blended with a non-photosensitive resin and / or a photosensitive resin. At present, from the viewpoint of environmental problems, organic solvents are almost no longer used as developers, and alkali developers are the mainstream, but when alkali developers are used, alkali-soluble non-photosensitive materials are used in photosensitive compositions. It is preferable to contain a resin.

  Here, the alkali-soluble non-photosensitive resin means a resin that has solubility in an alkali developer and does not have radical crosslinkability. For example, an acidic functional group such as a carboxyl group or a sulfone group. A resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, having a group. Specifically, acrylic resin, α-olefin / (anhydrous) maleic acid copolymer, styrene / (anhydrous) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer And an isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin, an α-olefin / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfonic acid copolymer is preferable. In particular, acrylic resins are preferably used because of their high heat resistance and transparency.

  Moreover, the photosensitive resin suitably used for the photosensitive composition according to the present embodiment means a resin having radical crosslinkability, and is a weight average having at least one ethylenically unsaturated double bond. Resins having a molecular weight of 5,000 to 100,000 can be suitably used. Specifically, a linear polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group has a (meth) acryl having an isocyanate group, an aldehyde group, an epoxy group, or the like that can react with the reactive functional group. Examples thereof include resins in which an ethylenically unsaturated double bond is introduced into the linear polymer by reacting a compound, cinnamic acid, or the like. In addition, a linear polymer having a reactive functional group such as an isocyanate group, an aldehyde group, or an epoxy group has a (meth) acrylic compound having a hydroxyl group, a carboxyl group, an amino group, or the like that can react with the reactive functional group. Examples thereof include a resin obtained by reacting an acid or the like and introducing an ethylenically unsaturated double bond into the linear polymer. In addition, (meth) acrylic compounds having a hydroxyl group such as hydroxyalkyl (meth) acrylate, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer A half-esterified product is also used.

<Active energy ray-curable polymerization initiator>
An active energy ray-curable polymerization initiator is added to the color filter coloring composition according to the present embodiment in order to cure the composition by ultraviolet irradiation or to form a filter segment by a photolithographic method. . The blending amount of the active energy ray-curable polymerization initiator is preferably 5 to 200% by weight based on the total amount of the pigment, and 10 to 150% by weight from the viewpoint of active energy ray curability and developability. Is more preferable.

  Examples of the active energy ray-curable polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 2-methyl-1- [4- (methylthio) phenyl]- Acetophenone-based active energy ray-curable polymerization initiators such as 2-morpholinopropan-1-one; Benzoin-based active energy ray-curable polymerizations such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal start Benzophenone-based active energy ray-curable polymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide; Thioxanthone-based active energy ray-curable polymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s- Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (tri (Loromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-) Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloro Triazine-based active energy ray-curable polymerization initiators such as methyl- (piperonyl) -6-triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine; borate-based active energy ray-curable polymerization initiation Carbazole-based active energy ray-curable polymerization initiator; imidazole-based active energy ray-curable polymerization initiator; and oxime ester An active energy ray-curable polymerization initiator or the like is used.

  The above active energy ray-curable polymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4 ′ -A compound such as diethylaminobenzophenone can also be used in combination.

  In the case of using a sensitizer, the blending amount of the sensitizer is preferably 3 to 60% by weight based on the active energy ray-curable polymerization initiator, and the active energy ray-curable and developable properties. From the viewpoint, it is more preferably 5 to 50% by weight.

<Solvent>
In the coloring composition for a color filter according to the present embodiment, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent is included to facilitate the formation of the segments.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3- Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m- Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyla Lucol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ter, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene group Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone Emissions, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, and the like, can be used alone or in combination.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition according to this embodiment. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie.

  Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  As a particularly preferred leveling agent, one kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule can be mentioned. Since this leveling agent has a hydrophilic group and has low solubility in water, it has a feature that when it is added to the coloring composition, its surface tension reducing ability is low. Among such leveling agents, those having good wettability to the glass plate in spite of low surface tension reducing ability are useful, and are sufficiently added in an amount that does not cause coating film defects due to foaming. What can suppress charging property can be preferably used.

  As the leveling agent, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used.

  Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts.

  Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Other ingredients>
The colored composition according to the present embodiment can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. 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.

  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 preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

[Removal of coarse particles]
The coloring composition containing each component described above can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist. In addition, a coloring resist disperse | distributes a coloring agent in the composition containing transparent resin, a monomer, a photoinitiator, and an organic solvent.

  The colored composition according to the present embodiment is preferably 5 μm or larger coarse particles, more preferably 1 μm or larger coarse particles, and even more preferably 0.5 μm or larger by means of centrifugation, sintered filter, membrane filter or the like. It is desirable to remove coarse particles and mixed dust.

  Thus, it is preferable that the coloring composition according to the present embodiment does not substantially contain particles of 0.5 μm or more. More preferably, the particle diameter is 0.3 μm or less (particle diameter by SEM).

  Next, a color filter according to the second embodiment of the present invention will be described.

  The color filter according to the second embodiment of the present invention can be produced by the printing method or the photolithography method using the colored composition according to the first embodiment of the present invention described above.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the composition of the coloring composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent 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 rays through a mask having a predetermined pattern provided in contact with or not in 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.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

  In order to increase the UV exposure sensitivity, the colored resist is applied and dried, and then water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to inhibit polymerization by oxygen. After forming a film for preventing the exposure, ultraviolet exposure can also be performed.

  The color filter according to the present embodiment can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the above-described colored composition can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  The color filter according to the present embodiment includes at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one green filter segment is the first aspect of the present invention described above. It forms using the coloring composition for color filters which concerns on this embodiment.

  The red filter segment can be formed using a normal red coloring composition. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Red pigments such as 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 are used.

  The red coloring composition includes C.I. I. Pigment Orange 43, 71, 73, etc. and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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 It can be used in combination with the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 are used. The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto.

  In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, the liquid crystal is injected from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or retardation film is bonded to the outside of the substrate Thus, a liquid crystal display panel can be manufactured.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  Hereinafter, synthesis examples of polyfunctional acrylates as photopolymerizable monomers, examples of preparing colored photosensitive compositions containing various photopolymerizable monomers, and comparative examples will be specifically described. The present invention is not limited to the embodiments, and various modifications can be made without departing from the spirit of the present invention. In the examples, “part” represents “part by weight”.

(Synthesis Example 1)
A five-necked reaction vessel with an internal volume of 1 liter is charged with 623 g of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) and 44 g of hexamethylene diisocyanate and reacted at 60 ° C. for 8 hours to have (meth) acryloyl groups A product containing polyfunctional acrylate (1) was obtained. The proportion of the polyfunctional acrylate (1) in the product is 45% by weight, and the remainder is occupied by other photopolymerizable monomers. In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(Synthesis Example 2)
A 5-liter reaction vessel with an internal volume of 1 liter is charged with 142 g of glycidyl methacrylate, 77 g of acrylic acid, 0.2 g of methoxyphenol, and 3 g of triphenylphosphine and reacted at 80 ° C. for 12 hours, 2-hydroxy-3-acryloylpropyl Methacrylate was obtained. Further, 490 g of a trimethylolpropane hexamethylene diisocyanate adduct [Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.)] was added to this and reacted at 60 ° C. for 8 hours to give a polyfunctional acrylate having a (meth) acryloyl group (2) A product containing was obtained. The proportion of the polyfunctional acrylate (2) in the product is 100% by weight. It was confirmed by the IR analysis that no isocyanate group was present in the reaction product.

(Synthesis of acrylic resin A and preparation of its solution)
The reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, 85.0 N, N-methyl methacrylate. A mixture of 95.0 parts of n-butyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction.

  After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. A cyclohexanone solution of acrylic resin A having a weight average molecular weight of about 30,000 and an acid value of 87 mgKOH / g was obtained.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, ethylene glycol monomethyl was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Acrylic resin A solution was prepared by adding ether acetate.

(Preparation of resin-type dispersant solution)
A commercially available resin type dispersant, SOLSPERSE 56000 manufactured by Nippon Lubrizol, and ethylene glycol monomethyl ether acetate were used to prepare a 40% by weight non-volatile solution and used as a resin type dispersant solution.

[Example 1]
11.0 parts of a zinc halide phthalocyanine-based green pigment (CI pigment green 58), 2.5 parts of the resin-type dispersant solution, 40.0 parts of the acrylic resin A solution, and ethylene glycol monomethyl ether acetate 46 After uniformly stirring and mixing 5 parts of the mixture, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then 5.0 μm Filtration through a filter produced a green pigment dispersion.

  Next, 40.0 parts of the green pigment dispersion, 22.4 parts by weight of the acrylic transparent resin, 2.9 parts by weight of the polyfunctional acrylate (1) synthesized in Synthesis Example 1 as a photopolymerizable monomer, a photopolymerization initiator ( Ciba Japan "Irgacure OXE-02") 0.2 parts, a mixture of cyclohexanone, ethylene glycol monomethyl ether acetate, and 34.5 parts of a mixed solution of ethyl-3-ethoxypropionate was stirred uniformly. After mixing, the mixture was filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 1.

[Examples 2 and 3]
As in Example 1, the polyfunctional acrylate (1) is used as a photopolymerizable monomer, and the addition amount is changed to the amount shown in Table 1 below. Alkali developable green resist materials 2 and 3 having the composition were prepared.

[Example 4]
An alkali-developable green resist material 4 having the composition shown in Table 1 below was obtained in the same manner as in Example 2 except that the amount of the green pigment dispersion was reduced to 20.0 parts.

[Example 5]
An alkali-developable green resist material 5 having the composition shown in Table 1 below was obtained in the same manner as in Example 2 except that the amount of the green pigment dispersion was increased to 50.0 parts.

[Example 6]
An alkali-developable green resist material 6 having the composition shown in Table 1 below was prepared in the same manner as in Example 1 except that the photopolymerizable monomer was changed to the polyfunctional acrylate (2) synthesized in Synthesis Example 2. .

[Examples 7 to 8]
Alkali development type having the composition shown in Table 1 below in the same manner as in Example 6 except that polyfunctional acrylate (2) was used as the photopolymerizable monomer and the addition amount was changed to the amount shown in Table 1 below. Green resist materials 7 to 8 were produced.

[Example 9]
An alkali-developable green resist material 9 having the composition shown in Table 1 below was obtained in the same manner as in Example 7 except that the amount of the green pigment dispersion was reduced to 20.0 parts.

[Example 10]
An alkali-developable green resist material 10 having the composition shown in Table 1 below was obtained in the same manner as in Example 7 except that the amount of the green pigment dispersion was increased to 50.0 parts.

[ Reference Example 1 ]
In the same manner as in Example 1 except that the photopolymerizable monomer was changed to a monomer containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toa Gosei Co., Ltd.) An alkali development type green resist material 11 having the composition shown in 1 was prepared.

[ Reference Examples 2 and 3 ]
A monomer containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toa Gosei Co., Ltd.) was used as a photopolymerizable monomer, and the addition amount was changed to the amount shown in Table 1 below. Except for, alkaline development type green resist materials 12 and 13 having the compositions shown in Table 1 below were prepared in the same manner as in Reference Example 1 .

[ Reference Example 4 ]
An alkali-developable green resist material 14 was obtained in the same manner as in Reference Example 2 except that the amount of the green pigment dispersion was reduced to 20.0 parts. The detailed composition is shown in Table 1 below.

[ Reference Example 5 ]
An alkali-developable green resist material 15 having the composition shown in Table 1 below was obtained in the same manner as in Reference Example 2 except that the amount of the green pigment dispersion was increased to 50.0 parts.

[Comparative Example 1]
Alkaline development having the composition shown in Table 2 below was carried out in the same manner as in Example 1 except that polyfunctional acrylate (1) was used as the photopolymerizable monomer and the addition amount was changed to the amount shown in Table 2 below. A green resist material 16 was prepared.

[Comparative Example 2]
Alkali development having the composition shown in Table 2 below was carried out in the same manner as in Example 6 except that polyfunctional acrylate (2) was used as the photopolymerizable monomer and the addition amount was changed to the amount shown in Table 2 below. A green resist material 17 was prepared.

[Comparative Example 3]
A monomer containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toa Gosei Co., Ltd.) was used as the photopolymerizable monomer, and the addition amount was changed to the amount shown in Table 2 below. In the same manner as in Example 11, except that the alkaline development type green resist material 18 having the composition shown in Table 2 below was produced.

[Comparative Example 4]
Alkaline development type having the composition shown in Table 2 below in the same manner as in Example 1 except that the photopolymerizable monomer was changed to caprolactone-modified dipentaerythritol hexaacrylate (“DPCA-30” manufactured by Nippon Kayaku Co., Ltd.). A green resist material 19 was produced.

[Comparative Examples 5 and 6]
Comparative Example 4 except that caprolactone-modified dipentaerythritol hexaacrylate (“DPCA-30” manufactured by Nippon Kayaku Co., Ltd.) was used as the photopolymerizable monomer and the addition amount was changed to the amount shown in Table 2 below. Similarly, alkali development type green resist materials 20 and 21 having the compositions shown in Table 2 below were prepared.

[Comparative Example 7]
In the same manner as in Example 2, except that a halogenated copper phthalocyanine green pigment (CI pigment green 36) was used instead of the halogenated zinc phthalocyanine green pigment (CI pigment green 58). An alkali developing resist material 22 having the composition shown in Table 2 below was obtained.

[Comparative Example 8]
Except for using a halogenated copper phthalocyanine green pigment (CI pigment green 36) in place of the halogenated zinc phthalocyanine green pigment (CI pigment green 58), the same as in Example 7, the following An alkali developing resist material 23 having the composition shown in Table 2 was obtained.

[Comparative Example 9]
Except for using a halogenated copper phthalocyanine green pigment (CI pigment green 36) in place of the halogenated zinc phthalocyanine green pigment (CI pigment green 58), the same as in Example 12, the following An alkali developing resist material 24 having the composition shown in Table 2 was obtained.

(Evaluation method)
Using the alkali developing resist materials 1 to 24 obtained in the above Examples and Comparative Examples, tests for confirming the voltage holding ratio, the brightness, and the occurrence of foreign matters were performed. These procedures are shown below.

(Voltage holding ratio measurement method)
The alkali developing resist materials 1 to 24 were applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the film thickness of the dry film was 1.8 μm, and exposed at an exposure amount of 50 mJ / cm ² . Thereafter, spray development was performed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, and baking was performed at 230 ° C. in an oven to obtain coated substrates of resist materials 1 to 24.

  After removing 0.05 g of the resist coating film from the obtained coated substrate, it was immersed in 1.5 g of liquid crystal (MLC-2041 manufactured by Merck Ltd.), aged in a 120 ° C. oven for 60 minutes, and at 4000 rpm. After centrifuging for 15 minutes, a supernatant liquid was collected to prepare a resist extraction liquid crystal sample liquid.

  On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are arranged facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap becomes 9 μm. did.

A resist extraction liquid crystal sample solution is injected between the cell gaps of this small cell, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V ₁ ] after 16.67 msec has elapsed after the voltage release, The measurement was performed with Toyo Technica VHR-1S.

  The measurement was repeated 5 times, and the measured cell voltages were averaged. And the voltage holding rate (%) was calculated | required from the following formula using the obtained cell voltage.

Voltage holding ratio (%) = ([V ₁ ] / 5) × 100
The evaluation criteria for the voltage holding ratio (%) are as follows.

◎: Voltage holding ratio of 95% or more ○: Voltage holding ratio of 90% or more and less than 95% △: Voltage holding ratio of 85% or more and less than 90% ×: Voltage holding ratio of less than 85% (Lightness measurement method)
Using the obtained alkali development type resist materials 1 to 24, a spin coater is used to change the rotational speed so that the dry film thickness becomes 0.62, 0.6, 0.58 in the CIE color system. Thus, three coated substrates were prepared.

  After coating and drying at 230 ° C. for 40 minutes in a hot air oven, the film thickness and the contrast ratio were measured, respectively, and the brightness and contrast ratio at a chromaticity y of 0.6 were determined from the three points by the primary correlation method. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

The results are shown in Table 3 below.

  From Table 3 above, it can be seen that when a halogenated zinc phthalocyanine green pigment is used, the brightness is superior to that of a halogenated copper phthalocyanine green pigment. On the other hand, the voltage holding ratio decreases when the zinc halide phthalocyanine green pigment is used, but it can be seen that the voltage holding ratio is improved by using a polyfunctional acrylate as the photopolymerizable monomer. Moreover, the improvement degree of a voltage holding ratio increases by increasing the addition amount of polyfunctional acrylate, and a high voltage holding ratio can be achieved.

  On the other hand, in Comparative Examples 4 to 6 in which an alkali development type green resist material was prepared using caprolactone-modified dipentaerythritol hexaacrylate as a photopolymerizable monomer, no improvement in voltage holding ratio was observed.

As described above, by using a predetermined photopolymerizable monomer as a photopolymerizable monomer that is a component of the photosensitive composition, an alkali developing resist material containing a zinc halide phthalocyanine green pigment excellent in voltage holding ratio is obtained. Can be produced.
Hereinafter, the invention described in the scope of claims of the present application will be appended.
[1]
A photosensitive coloring composition containing a green coloring agent containing a halogenated zinc phthalocyanine pigment, a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin, an active energy ray-curable polymerization initiator, and a solvent. A voltage-retaining ratio of a liquid crystal display device including a color filter obtained by using the photosensitive coloring composition is 90% or more, and a photosensitive coloring composition for a color filter.
[2]
The photosensitive coloring composition for color filters according to [1], wherein the content of the zinc halide phthalocyanine pigment is 20 to 100 parts by weight with respect to 100 parts by weight of the green colorant.
[3]
The photopolymerizable monomer includes a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and the number of urethane groups of the polyfunctional urethane acrylate is 0.7. × ¹⁰ -3 mol / g or more, the double bond groups is characterized in that at 4.5 × ¹⁰ -3 mol / g or more [1] or a color filter for photosensitive coloring composition according to [2] .
[4]
The photosensitive coloring composition for color filters according to [3], wherein the content of the photopolymerizable monomer in the solid content of the coloring composition is 15% by weight or more and 45% by weight or less.
[5]
The photosensitive coloring composition for a color filter according to [1] or 2, wherein the photopolymerizable monomer contains dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
[6]
The photosensitive coloring composition for color filters according to [3], wherein the content of the photopolymerizable monomer in the solid content of the coloring composition is 10% by weight or more and 25% by weight or less.
[7]
A color filter comprising a green pixel formed using the photosensitive coloring composition according to any one of [1] to [6].
[8]
[7] A liquid crystal display device comprising the color filter according to [7].

Claims (4)

A photosensitive coloring composition containing a green coloring agent containing a halogenated zinc phthalocyanine pigment, a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin, an active energy ray-curable polymerization initiator, and a solvent. there, the voltage holding ratio of the liquid crystal display device comprising a color filter obtained by using the photosensitive coloring composition Ri der 90%
The photopolymerizable monomer includes a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and the number of urethane groups of the polyfunctional urethane acrylate is 0.7. × 10 ⁻³ mol / g or more, the number of double bond groups is 4.5 × 10 ⁻³ mol / g or more,
Wherein the photopolymerizable monomer for color filters photosensitive coloring composition content, characterized in der Rukoto 15 wt% or more 56 wt% or less in the solid content of the colored composition.   The photosensitive coloring composition for a color filter according to claim 1, wherein the content of the zinc halide phthalocyanine pigment is 20 to 100 parts by weight with respect to 100 parts by weight of the green colorant. Color filter characterized by comprising a green pixel formed using a photosensitive coloring composition according to claim 1 or 2. A liquid crystal display device comprising the color filter according to claim 3 .