JP5410183B2 - Green coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a green coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed 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 is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in 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.

  Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is further formed thereon. ing. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed 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, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  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, it is indispensable to prepare a pigment dispersion that is made as close as possible to primary particles by performing a finer treatment of the pigment. As a result, scattering of light 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. Therefore, it is possible to create a color filter with high brightness and high contrast. It becomes possible.

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

  As a method to solve these problems, zinc halide phthalocyanine is a colorant that exhibits a clear color tone and a wide color display area and has a high coloring power, in which the central metal is replaced with zinc from the current copper halide phthalocyanine green pigment. A green pigment is disclosed in Patent Document 1.

  In addition to the brightness / contrast ratio, a voltage holding ratio is an index that represents the display performance of a liquid crystal display element (LCD). Liquid crystal is a highly insulating material, and when polar compounds remaining in the color filter composition elute into the liquid crystal cell, the voltage between the electrodes decreases, causing a decrease in voltage holding ratio and causing display unevenness. This causes alignment failure and the like, and causes a decrease in performance as a liquid crystal display element. Therefore, the coloring composition is required to be insoluble in liquid crystals.

  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 high solubility compared to other pigment types, so that it is also easily extracted into 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.

In addition, due to this high acidity, it is difficult to ensure dispersion stability of halogenated zinc phthalocyanine green pigments as compared with other pigment types, and there is a phenomenon that crystal foreign matter is generated during storage over time. It can be seen. When this crystalline foreign material is generated, a good coating film cannot be formed and the coloring composition becomes unsuitable.

  Patent Document 2 discloses a method for adding various compounds such as an epoxy group-containing compound and an oxetane ring-containing compound as a method for improving the voltage holding ratio when using a pigment other than a conventionally used zinc halide phthalocyanine green pigment. Is disclosed.

  However, the halogenated zinc phthalocyanine green pigment, which has higher acidity than the halogenated copper phthalocyanine green pigment, has a good voltage holding ratio, does not cause display unevenness and orientation failure, and has good dispersion stability over time. It was very difficult to obtain a green coloring composition for a color filter.

JP 2004-70342 A JP 2000-292920 A

  The object of the present invention is to improve the developability, voltage holding ratio, and generation of crystal foreign matter, which were problems when using a halogenated zinc phthalocyanine green pigment having excellent lightness, and to provide a color having lightness superior to conventional copper phthalocyanine green pigments. It is to provide a green coloring composition for a filter, and a color filter using them.

The problems include a green colorant [A] containing at least a zinc halide phthalocyanine green pigment, an epoxy compound [B], a photopolymerizable monomer [C], a photopolymerization initiator [D], and an organic solvent. [E], and the epoxy compound [B] is 23 to 300 when the weight of the zinc halide phthalocyanine green pigment in the green coloring composition is 100 parts by weight. It is solved by a green coloring composition for a color filter, which is contained by weight and has an epoxy equivalent of 100 to 177 (g / eq: molecular weight per epoxy group = molecular weight ÷ epoxy group number).

The present invention further relates to the green coloring composition for a color filter, further comprising a binder resin [F].

In the present invention, the binder resin [F] has an acid value in the range of 20 to 300 mgKOH / g and a weight average molecular weight in the range of 5,000 to 100,000. Relates to the composition.

  The present invention also relates to a color filter comprising a green filter segment formed from the green composition for a color filter.

  According to the method of the present invention, it is possible to produce a green coloring composition for a color filter containing a zinc halide phthalocyanine green pigment, which does not generate crystalline foreign matters and has excellent developability and voltage holding ratio. As a result, it is possible to provide a green coloring composition for a color filter that is superior in brightness to conventional copper halide phthalocyanine green pigments, and a color filter using them.

First, various components of the green coloring composition for a color filter of the present invention will be described.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.

<Green colorant [A]>
The green coloring composition for a color filter of the present invention is characterized by containing a green coloring agent [A] containing at least a zinc halide phthalocyanine green pigment.

  A typical zinc halide phthalocyanine green 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 green pigment, it is possible to obtain a high brightness not obtained with other green pigments. Furthermore, what was obtained by the well-known manufacturing method can be used. In particular, the amount of acidic functional groups on the pigment surface is preferably 100 μmol when measured using n-hexylamine as a basic substance by the method described in Coloring Materials, 67 [9], 547-554 (1994). / G or more, more preferably 200 μmol / g or more can be used.

In addition, since the halogenated zinc phthalocyanine green pigment shows high acidity and has higher solubility than other pigment types, the voltage holding ratio is likely to decrease, and it is difficult to ensure pigment dispersion stability. Therefore, even when other substances are mixed with a green coloring composition containing a halogenated zinc phthalocyanine green pigment, the pigment dispersion system becomes easily unstable, and the halogenated zinc phthalocyanine green pigment easily crystallizes. In the case of containing such a substance, there is a problem that a salt with a halogenated zinc phthalocyanine green pigment showing high acidity is precipitated as a foreign substance.
As described above, it is a problem in producing a color filter using a halogenated zinc phthalocyanine green pigment that suppresses the generation of crystalline foreign matters and improves the voltage holding ratio.

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

  Other green pigments that can be used in combination include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, and 37. 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 Mention may be made of the yellow pigments such as 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.

  In the green coloring composition according to the present invention, the concentration of the green colorant [A] containing the halogenated zinc phthalocyanine green pigment with respect to all nonvolatile components needs to be 10 to 90% by weight from the viewpoint of obtaining sufficient color reproducibility. More preferably, it is 15 to 85% by weight, and most preferably 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility cannot be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is decreased, and the color composition is stabilized. Sexuality gets worse.

  The preferred colorant ratio is, for example, 20 to 100% by weight of the halogenated zinc phthalocyanine green pigment, 0 to 80% by weight of the halogenated copper phthalocyanine green pigment, based on the total weight of the green colorant [A], yellow The pigment is 0 to 50% by weight.

  More preferably, based on the total weight of the green colorant [A], the halogenated zinc phthalocyanine green pigment is 50 to 90% by weight, the copper halide phthalocyanine green pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. %. The chromaticity region can be expanded by such a composition ratio of the pigment.

  The green coloring composition of the present invention using a halogenated zinc phthalocyanine green pigment is applied to a glass substrate or the like so as to have the same chromaticity as that of a green coloring composition using a 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 green pigment in the vicinity of about 530 nm from about 450 nm. In particular, the transmittance peak shows a transmittance as high as about 5% and a value of about 90%. 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 could not be obtained with a colored composition using a halogenated copper phthalocyanine green pigment such as CI Pigment Green 7 can be obtained.

  The pigment used in the green coloring composition of the present invention can be subjected to a salt milling process and can be used in a refined product, and is preferably used in a refined product.

  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 close to 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 distribution width is wide.

  It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the green pigment used for the green coloring composition of this invention is the range of 20-100 nm. When it becomes smaller than 20 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 100 nm, a sufficient contrast ratio cannot be obtained. 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 functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. 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. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene 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, liquid polypropylene glycol, or the like is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 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 more preferably partially soluble in the 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 of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (1).

General formula (1):
P-Lm formula (1)
(However,
P: Organic pigment residue L: Basic substituent, acidic substituent, compound having a phthalimidomethyl group which may have a substituent, etc.
m is an integer of 1 to 4)

Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the 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 with respect 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 (1), 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, copper halide phthalocyanine, and metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, and violanthrone;
Quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; and metal complex pigments.
In the green coloring composition for a color filter of the present invention, it is also preferable to use a dye derivative for the purpose of improving the dispersibility of the pigment.

<Epoxy compound [B]>
The epoxy compound [B] in the present invention refers to a compound having an epoxy group, and the epoxy group undergoes a thermosetting reaction at the time of baking, which is a color filter manufacturing process, and the coating film surface / inside is crosslinked to form a zinc halide. Elution of impurities derived from phthalocyanine green pigment or zinc halide phthalocyanine green pigment into the liquid crystal phase can be suppressed. The epoxy compound may be a low molecular compound or a high molecular compound, and representative examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy. Resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oil; brominated derivatives of the above epoxy resins, tris (glycidylphenyl) methane, Triglycidyl isocyanurate etc. are mentioned. Among them, bisphenyl A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, cycloaliphatic type epoxy resin, glycidyl ester type resin, glycidylamine type resin, tris (glycidylphenyl) methane This is preferable in that the cured density is high and the adverse effect on the developability of the colored composition is small.

  Examples of preferred commercially available epoxy compounds that can be used in the present invention include Nagase Chemtex EX111, EX201, EX411, EX901, Nippon Kayaku EPPN501H, Japan Epoxy Resin JER152, and the like.

  The epoxy compound [B] is added in an amount of 10 to 300 parts by weight based on 100 parts by weight of the zinc halide phthalocyanine green pigment in the green coloring composition. When the addition amount is less than 10 parts by weight, the cured density of the film is low, and the effect of improving the voltage holding ratio is reduced. When the amount exceeds 300 parts by weight, the addition amount of a photopolymerizable monomer, a photopolymerization initiator and the like is limited, and sufficient developability cannot be secured, and stability over time becomes a problem.

  The epoxy equivalent in the present invention refers to a value defined by “molecular weight / number of epoxy groups: unit g / eq” obtained by calculation from the chemical formula of the epoxy compound, that is, a molecular weight per one epoxy group. In the present invention, a range of 100 to 500 is preferable, and a range of 100 to 250 is more preferable. When the epoxy equivalent is less than 100, the curability is high and the cross-linking density of the film becomes too high, the shrinkage at the time of curing increases, and the flatness of the film cannot be obtained. When the epoxy equivalent exceeds 500, the curability is insufficient and the effect of improving the voltage holding ratio is reduced.

  Moreover, in order to accelerate | stimulate hardening of an epoxy compound, you may use an epoxy hardener together. Typical epoxy curing agents include acid anhydride curing agents and amine curing agents, but amine curing agents have a high reaction rate and are difficult to stabilize in a one-part system. In the present invention, it is difficult to ensure dispersion stability due to poor compatibility with the zinc phthalocyanine pigment, and it is difficult to ensure dispersion stability. An agent is desirable. Acid anhydride epoxy curing agents include maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid Examples of the acid anhydride are as follows. Among these, from the viewpoint that a dense cross-linked structure can be constructed, it is preferable that one molecule has two or more anhydride groups, and optical characteristics such as good short wavelength transmission. And a saturated hydrocarbon polyfunctional acid anhydride such as cyclohexanetetracarboxylic dianhydride is more preferable from the viewpoint of maintaining a high voltage holding ratio of the liquid crystal.

<Binder resin [F]>
The colored composition of the present invention preferably contains a binder resin [F]. By including the binder resin [F], the dispersion stability of the green coloring composition of the present invention becomes better, and when the color material layer of the color filter is formed using the coloring composition, there are few pigment aggregates, A colorant layer with good developability and pattern shape can be obtained.

  The binder resin [F] includes thermoplastic resin (F1), thermosetting resin (F2), alkali-soluble vinyl resin (F3) copolymerized with an acidic group-containing ethylenically unsaturated monomer, and ethylenically unsaturated resin. The energy ray curable resin (F4) having a saturated active double bond is preferable, and the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. .

  The thermoplastic resin (F1) as the binder resin [F] includes, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Can be mentioned.

  Examples of the thermosetting resin (F2) as the binder resin [F] include benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  When the green coloring composition for color filter of the present invention is used in the form of an alkali developing type colored resist, an acid group-containing ethylenically unsaturated monomer such as (meth) acrylic acid is copolymerized as the binder resin [F]. It is preferable to use an alkali-soluble vinyl resin (F3).

  Further, as the binder resin [F], an energy ray curable resin (F4) having an ethylenically unsaturated active double bond can also be used. As a method for producing the resin (F4), as a precursor of the resin (F4), for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group is prepared. 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 a (meth) acrylic compound having a reactive substituent such as an epoxy group or an epoxy group or cinnamic acid Or a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer having a hydroxyl group such as hydroxyalkyl (meth) acrylate (meta There is a method of half-esterification with an acrylic compound.

  Among the binder resins [F], those having both alkali-soluble performance and energy beam curing performance can be used as those having both performance of the resin (F3) and the resin (F4).

In order to disperse the pigment preferably, the weight average molecular weight (Mw) of the binder resin [F] is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000. Preferably, it is the range of 5,000-30,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
When the weight average molecular weight (Mw) of the binder resin [F] is 100,000 or more, the interaction between the resins becomes strong and the viscosity of the green coloring composition becomes high, so that the handling tends to be difficult. Further, when the weight average molecular weight (Mw) is 5,000 or less, problems may occur in developability and adhesion to a substrate such as glass.

  The binder resin [F] can be used in an amount of 0 to 500 parts by weight based on the total weight of the green colorant [A]. The amount is preferably 30 to 500 parts by weight, and if it is less than 30 parts by weight, developability, film formability and various resistances tend to be insufficient, and if it exceeds 500 parts by weight, the pigment concentration is low and color characteristics cannot be expressed.

In addition, the binder resin [F] is a fat that acts as an affinity group for a pigment adsorbing group and an alkali-soluble group during development, a pigment carrier, and a solvent from the viewpoint of pigment dispersibility, developability, and heat resistance. Since the balance between the group and the aromatic group is important for pigment dispersibility, developability, and durability, the acid value is preferably within the range of 20 to 300 mgKOH / g.
More preferably, the acid value is in the range of 50 to 150 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.
Furthermore, when the acid value is in the range of 50 to 150 mgKOH / g, the dispersion stability of the green colored composition becomes good, and the suppression of crystal foreign matter becomes better.

<Photopolymerizable monomer [C]>
The photopolymerizable monomer [C] contained in the green colored composition for color filters of the present invention is an ethylenically unsaturated double bond that forms a transparent resin by curing the colored composition by ultraviolet irradiation. The photopolymerizable monomer includes a low polymer having an average molecular weight of about 1000, generally called an oligomer, and having an ethylenically unsaturated double bond.
The blending amount when using the photopolymerizable monomer [C] is preferably 10 to 300% by weight based on the total amount of the green colorant [A], from the viewpoint of photocurability and developability. More preferably, it is 10 to 200% by weight.

As the photopolymerizable monomer [C],
Methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tricyclodecanyl Monofunctional (meth) acrylates such as (meth) acrylate;
Bifunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate;
Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate Functional (meth) acrylate;
1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, and epoxy (meth) acrylate which is a reaction product of an epoxy compound such as phenol novolac resin and (meth) acrylic acid;
Various (meth) acrylic acid esters modified with polyester, polyurethane, isocyanurate, methylolated melamine, etc .; and (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, ( Examples include monomers other than (meth) acrylates such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile, and these can be used alone or in combination of two or more. However, it is not necessarily limited to these.

<Photopolymerization initiator [D]>
A photopolymerization initiator [D] is added to the green coloring composition for a color filter of the present invention when the composition is cured by ultraviolet irradiation or a filter segment is formed by a photolithography method. The blending amount when using the photopolymerization initiator [D] is preferably 5 to 200% by weight based on the total amount of the green colorant [A], and 10 to 10% from the viewpoint of photocurability and developability. More preferably, it is 150% by weight.

As the photopolymerization initiator [D],
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal;
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -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-trichloromethyl- (piperonyl) -6-triazine, and 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
A borate photopolymerization initiator; a carbazole photopolymerization initiator; an imidazole photopolymerization initiator; and an oxime ester photopolymerization initiator are used.

The above photopolymerization initiators are used alone or in combination of two or more, but as a sensitizer,
α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, Compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 4,4′-diethylaminobenzophenone can also be used in combination.

  The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the photopolymerization initiator [D] contained in the colored composition, from the viewpoint of photocurability and developability. More preferably, it is 5 to 50% by weight.

<Organic solvent [E]>
Furthermore, in the green coloring composition for a color filter of the present invention, 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. An organic solvent [E] can be included to facilitate the formation of the filter segment.
Examples of the organic solvent [E] include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and 2-heptanone. 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-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrole , 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 , Ethylene glycol monohexyl ether, ethylene glycol mono Cyl 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 glycol 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, acetic acid Iso Mill, isobutyl acetate, propyl acetate, dibasic esters, and the like, used alone or in admixture

<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 of the present invention. 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.

<Other ingredients>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. 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% by weight based on the green colorant [A] in the coloring composition.

  Examples of the adhesion improver 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 (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the green colorant [A] in the coloring composition.

<Dispersion>
The green coloring composition of the present invention comprises a green colorant [A] containing at least a zinc halide phthalocyanine green pigment, preferably together with a dye derivative and / or a dispersion aid, together with a binder resin [F] and an organic solvent [E]. In a colorant carrier such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. The green coloring composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a resin-type dispersant and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, the green coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid. When is used, a color filter having a high spectral transmittance can be obtained.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type 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 alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Water-soluble such as oil-based dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester, Polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, 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.

<Removal of coarse particles>
The green coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter, etc., and coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust.
Thus, it is preferable that a green coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less. (Particle size by SEM)

<Color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  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 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 coloring composition prepared as a solvent developing type or alkali developing type colored resist material is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. 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 material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above 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, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention 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.

  Next, the color filter of the present invention will be described. The color filter of the present invention 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 a green coloring composition for the color filter of the present invention. It is formed using.

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, 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, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, Red pigments such as 255, 264, 272, or 279 are used. The red coloring composition includes C.I. I. Pigment orange 38, 43, 71, 73 and / or the like, 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. Further, 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, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
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.

EXAMPLES 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”.
In the examples and comparative examples, “part” means “part by weight”. Mn and Mw mean a number average molecular weight and a weight average molecular weight, respectively.

(Synthesis of acrylic resin A and preparation of its solution)
In a reaction vessel, 800 parts of cyclohexanone was 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 parts of methyl methacrylate, n- A mixture of 95.0 parts of 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. The acid value and weight average molecular weight of the synthesized resin are shown in Table 1.

(Synthesis of acrylic resins B to E and preparation of the solution)
Acrylic resins B to E were synthesized in the same manner as the acrylic resin A synthesis method with the monomer composition, initiator (azobisisobutyronitrile) and its amount (parts by weight) shown in Table 1, and their solutions Was prepared. The acid value and weight average molecular weight of the synthesized resin are shown in Table 1.

However, the abbreviations in Table 1 are as follows.
MA: methacrylic acid MMA: methyl methacrylate nBMA: n-butyl methacrylate AIBN: azobisisobutyronitrile

(Preparation of resin-type dispersant solution)
A commercially available resin type dispersant, “EFKA4300” manufactured by Ciba Japan Co., Ltd., 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.

(Preparation of green pigment dispersion 1)
11.0 parts of a zinc halide phthalocyanine 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 5 parts of the mixture was stirred and mixed uniformly, the mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5.0 μm filter. To prepare a green pigment dispersion 1.

(Preparation of green pigment dispersion 2)
In the same manner as in Green Pigment Dispersion 1, 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), a green color was obtained. Pigment dispersion 2 was prepared.

[Examples 1 to 15 and Comparative Examples 1 to 12]
After stirring and mixing each composition shown in Table 2 and its amount (parts by weight) uniformly, the mixture was filtered with a 1.0 μm filter to obtain alkali-developing green resist materials 1 to 27, Each was evaluated in the following manner.
However, Examples 3, 4, 9, and 15 are reference examples.

However, the abbreviations in Table 2 are as follows.
Photopolymerizable monomer [C]: dipentaerythritol hexaacrylate Photopolymerization initiator [D]: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba “Irgacure 907” manufactured by Japan
Sensitizer: 4,4′-diethylaminobenzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)
Organic solvent [E]: ethylene glycol monomethyl ether acetate Epoxy compounds A to G: Table 3 shows each.
Acrylic compounds A to C: are shown in Table 3, respectively.

(Evaluation method)
Using the obtained alkali development type green resist materials 1 to 27, voltage holding ratio, brightness, confirmation of occurrence of foreign matter, and evaluation on developability were performed. The experimental procedure is shown below.

(Voltage holding ratio measurement method)
Each alkali-developable green resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the dry film thickness was 1.8 μm and exposed at an exposure amount of 50 mJ / cm ^2. Spray development was carried out with a 0.2 wt% sodium carbonate aqueous solution at 30 ° C. for 30 seconds, followed by baking at 230 ° C. in an oven to obtain a coated substrate of each resist material. 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 & Co., Inc.), aged in a 120 ° C. oven for 60 minutes, and at 4000 rpm. After centrifugation 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 placed 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 is 9 μm. did. A resist-extracted liquid crystal sample solution is injected into the small cell between the cell gaps, 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, Measured 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) × 1 0 0
The evaluation criteria for the voltage holding ratio (%) are as follows.
◎: 95% or more ○: 90% or more and less than 95% △: 85% or more and less than 90% ×: less than 85%

(Brightness measurement method)
Using each spin-coater for each alkali-developable green resist material, the chromaticity y with a C light source in the CIE color system of the dried coating film is changed to 0.62, 0.60, 0.58 by changing the rotation speed. Three coating substrates were prepared respectively by changing the film thickness. After application, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the lightness at a chromaticity y of 0.6 was determined from the three points of data by the primary correlation method. The chromaticity was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

(Observation method of crystal foreign matter)
30 ml of each alkali-developable green resist material was allowed to stand in an environment of 40 ° C. for 7 days, filtered using a 5 μm pore size filter attached to a syringe, and then washed with 20 ml of ethylene glycol monomethyl ether acetate. The foreign matter remaining on the filter was observed and evaluated with a microscope. The evaluation criteria are as follows.
○: No foreign matter is observed Δ: Five or less foreign matters are observed ×: Many foreign matters are observed exceeding five

(Developability evaluation)
Each alkali-developable green resist material is spin-coated on a 10 × 10 cm transparent glass substrate, pre-baked at 70 ° C. for 20 minutes to form a coating film having a dry film thickness of about 2.0 μm, and then an exposure dose of 50 mJ / cm ² was exposed to UV light, 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao) and 99.7% by weight of water. The time (T1) in which the entire pattern of the unexposed area was dissolved was calculated with% alkali developer, and the development was extended to a time 1.5 times as long as T1.
At the development end point, the case where there was no pattern defect in the exposed area was marked with ◯, and the case where the pattern defect was marked with x.

The results are shown in Table 2.
Examples 1 to 15 include a green colorant [A] containing a zinc halide phthalocyanine green pigment, and an epoxy compound having an epoxy equivalent of 100 to 500 is used, and the addition amount of the epoxy compound is a halogenated zinc phthalocyanine green. 10 to 300 parts by weight with respect to 100 parts by weight of the pigment, the optimum addition amount, and thus high brightness and excellent results in voltage holding ratio (%) evaluation, foreign matter evaluation and developability evaluation. It was. In particular, Examples 1 to 3, 5, and 6 resulted in a satisfactory voltage holding ratio (%) because an epoxy compound having an epoxy equivalent in the range of 100 to 250 was sufficiently added.
Further, Examples 7 to 15 further including a binder resin [F] showed not only the voltage holding ratio (%) but also excellent developability, and further the resin acid value was 50 to 150 mgKOH / g, By using a resin having a weight average molecular weight of 5,000 to 100,000, it was possible to produce a green colored composition which was excellent in developability and further in terms of crystalline foreign matter.

On the other hand, Comparative Examples 1 to 5 in which no epoxy compound is added, Comparative Example 7 in which the addition amount of the epoxy compound is small, and Comparative Example 8 in which an epoxy compound having a high epoxy equivalent is used are all voltage holding ratios (%). There was no improvement. In Comparative Example 6, there was a problem in developability because the amount of the epoxy compound added was excessive.
In Comparative Examples 9 to 11, an acrylic compound having thermosetting properties was used in the same manner as the epoxy compound, but the effect of improving the voltage holding ratio was not as high as that of the epoxy compound, and there was a problem with either crystalline foreign matter or developability. It was seen.
In Comparative Example 12, since no halogenated zinc phthalocyanine green pigment was used, there was no problem in voltage holding ratio (%) and generation of crystal foreign matter, but the brightness was low.

As described above, the use of an epoxy compound having an epoxy equivalent in the range of 100 to 500, and the condition that the addition amount of the epoxy compound is 10 to 300 parts by weight with respect to 100 parts by weight of the halogenated zinc phthalocyanine green pigment. Thus, a green coloring composition for a color filter containing a zinc halide phthalocyanine green pigment that has good developability, suppresses the generation of crystalline foreign matters, and has an excellent voltage holding ratio can be produced.

Claims (4)

A green colorant [A] containing at least a zinc halide phthalocyanine green pigment, an epoxy compound [B], a photopolymerizable monomer [C], a photopolymerization initiator [D], and an organic solvent [E] And a green coloring composition (except for a solid-state imaging device) , wherein the epoxy compound [B] has a weight of 100 zinc halide phthalocyanine green pigment in the green coloring composition. 23 to 300 parts by weight in terms of parts by weight, and 100 to 177 epoxy equivalent (g / eq: molecular weight per epoxy group = molecular weight / number of epoxy groups) Green coloring composition.   Furthermore, binder resin [F] is contained, The green coloring composition for color filters of Claim 1 characterized by the above-mentioned.   The green coloring composition for a color filter according to claim 2, wherein the binder resin [F] has an acid value in the range of 20 to 300 mgKOH / g and a weight average molecular weight in the range of 5,000 to 100,000. object.   A color filter comprising a green filter segment formed from the green composition for a color filter according to claim 1.