JP2010032698A - Coloring curable composition for color filter, color filter, method for manufacturing color filter, and liquid crystal display element - Google Patents

Abstract

The present invention provides a color curable composition for a color filter, a color filter, a method for producing the same, and a liquid crystal display element capable of suppressing a surface deterioration caused by coating and forming a colored pattern with few defects.
(A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F) represented by the general formula (I). A colored curable composition for a color filter containing 0.02 to 10% by mass of a surfactant containing a structural unit represented by formula (II) as a copolymerization component. In the formula, R ⁰¹ represents a hydrogen atom or an alkyl group, and R ¹ represents a single bond or a linking group containing an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom. n is 1 to 10, m is 2 to 14, l is an integer of 0 to 10, p is 0 to 20, q is 0 to 20, r is an integer of 0 to 20, and p, q, and r are It is never 0 at the same time.
[Selection figure] None

Description

  The present invention relates to a colored curable composition, a color filter, a method for producing a color filter, and a liquid crystal display element.

  A color filter constituting a liquid crystal display (LCD), a color image pickup tube element (CCD), etc. is composed of a solvent dispersion composition of a colorant such as an organic pigment and an inorganic pigment, a binder resin and / or a monomer, and a photopolymerization initiator. And a colored photosensitive composition containing other components, which are manufactured by a photolithographic method including a step of coating and drying on a transparent substrate to form a coating film having a thickness of about 1 μm to 3 μm. .

In the manufacture of liquid crystal display devices, it is inevitable that the size of the substrate, including the thin film transistor (TFT) substrate and the color filter substrate, will increase. In recent years, at least one side has a length of 1000 mm or more. The above substrates are mainstream. Examples of such a substrate include substrates of 960 mm × 1100 mm, 1100 mm × l250 mm, 1100 mm × 1300 mm, 1500 mm × 1800 mm, 1800 mm × 2000 mm. On the other hand, the method of applying a curable composition to a substrate has also changed with the trend of increasing the substrate size.
When the substrate size is increased and the length of at least one side becomes 1000 mm or more, in order to improve the use efficiency of the curable composition, instead of the conventional spin coating method, “non-rotating coating” This method has become the mainstream. The use of a method called casting coating (hereinafter referred to as slit coating) that does not use spin coating has been studied. The slit coating method is a method suitable for forming a thin film on a large-sized substrate, and is a coating that discharges a coating liquid from the slit and forms a coating film having a desired film thickness on the surface of the transparent substrate while moving the slit. Is the method. However, due to the mechanism, stripe-shaped unevenness (straight unevenness) is likely to occur in the direction perpendicular to the direction of movement of the slit, and the outer periphery of the coating film rises, and the edge bulge becomes thicker than the center of the substrate, There is a drawback in that it is easy to cause coating failures such as moy unevenness, VCD unevenness, HP-pin marks, and edge bulge, and it is difficult to ensure uniformity of the entire screen.

  Further, there is a problem that pinholes (white spots) occur if the drying property and surface tension of the coating solution are not appropriate regardless of the coating method.

Various attempts have been made in the past to solve the problem of non-uniformity of the coating film in the spin coating method and the slit coating method. For example, a fluorosurfactant containing tetrafluoroethylene as a copolymerization component is used. A method for producing a liquid crystal display using a photosensitive resin composition (for example, see Patent Document 1) and a compound containing a fluorine-based or silicone-based compound having specific physical properties has been proposed (for example, (See Patent Document 2).
Although these compounds show some improvement in small-area coating, there is a problem that when the large-area coating film is formed by the slit coat coating method or the like, moya unevenness or edge unevenness occurs. Improvement was desired.
JP 2002-40650 A Japanese Patent No. 4034272

This invention is made | formed in view of said background art, and makes it a subject to achieve the objective shown below.
An object of the present invention is to provide a colored curable composition for a color filter, which is capable of forming a colored film with few defects and suppressing occurrence of coating failure even when slit coating is applied to a large area. .
Another object of the present invention is a color filter that uses the above-mentioned colored curable composition, has a good surface shape, and has excellent uniformity and manufacturing suitability for a colored layer having a colored pattern with few defects, An object of the present invention is to provide a method for producing the color filter and a liquid crystal display device including the color filter.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a surfactant having a specific structure, and have completed the present invention.
That is, the object of the present invention is achieved by the following means.

  The colored curable composition for color filters of the present invention comprises (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F ) In the composition, 0.02 to 10 mass of a surfactant containing at least one of the structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (II) as a copolymerization component. % Content.

In the general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other. R ¹ represents a single bond or a linking group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.
n represents an integer of 1 to 10, m represents an integer of 2 to 14, and l represents an integer of 0 to 10. a shows the mole percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
In the general formula (II), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁰¹ may be the same or different from each other that there are multiple. p is an integer of 0 to 20, q is an integer of 0 to 20, r is an integer of 0 to 20, and p, q, and r are not 0 at the same time. b shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

Here, the (F) surfactant is preferably a compound containing 10 to 50% by mass of the structural unit represented by the general formula (I).
Moreover, as said (D) solvent used for the colored curable composition for color filters of this invention, the mixture of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate is preferable, (A) As a coloring agent The pigment is preferably coated with a resin.

The color filter of the present invention has a colored pattern formed on the substrate by the colored curable composition for a color filter of the present invention.
The manufacturing method of the color filter of this invention has a coloring pattern formation process including the process of apply | coating the colored curable composition for color filters of this invention by the said slit coating method.
The liquid crystal display element of the present invention includes a color filter obtained by the method for producing a color filter of the present invention.

According to the present invention, it is possible to provide a colored curable composition for a color filter that is capable of forming a colored film with few defects and suppressing occurrence of coating failure even when slit coating is applied to a large area. .
Further, according to the present invention, a color filter using the above colored curable composition, having a good surface shape and having a colored pattern having few defects and excellent uniformity and manufacturing suitability of the colored layer, the color A filter manufacturing method and a liquid crystal display element including the color filter can be provided.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In addition, an ethylene oxide group may be expressed as “EO” and a propylene oxide group may be expressed as “PO”.

<Colored curable composition for color filter>
The colored curable composition for color filters of the present invention comprises (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F ) A surfactant containing at least one of a structural unit (repeating unit) represented by the following general formula (I) and a structural unit represented by the following general formula (II) as a copolymerization component is added to the composition in an amount of 0. It contains 02-10 mass%, It is characterized by the above-mentioned.
The colored curable composition of the present invention contains the components (A) to (F) described above, so that the surface tension of the colored curable composition is reduced and wettability to the coated surface such as a substrate is improved. The liquid properties (particularly fluidity) when used as a coating liquid are improved, and the uniformity of coating thickness and the liquid-saving property can be improved. In other words, the wettability to the substrate is improved by controlling the contact angle at the interface between the substrate and the coating liquid, and the appropriate coatability is imparted by the surfactant, Since the drying property is improved, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to form a film with a uniform thickness with small thickness unevenness, which is caused by nonuniform coating film thickness. It is possible to greatly reduce coating failures such as mist and edge swelling.
Hereinafter, each component of (A)-(F) is demonstrated in detail.

[(F) Surfactant containing at least one of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) as a copolymerization component]
The colored curable composition of the present invention comprises (F) a surfactant containing at least one of a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) as a copolymerization component. Containing. Hereinafter, this surfactant is appropriately referred to as “specific fluorine-containing surfactant”.
(F) The specific fluorine-containing surfactant includes a structural unit represented by the general formula (I) having a fluoroalkyl group, a structural unit represented by the general formula (II) having an alkyleneoxy group, and , If desired, a copolymer comprising other structural units copolymerizable therewith.
(Structural unit represented by general formula (I))

In the general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁰¹ may be the same or different from each other that there are multiple.
R ¹ is a single bond or an oxygen atom, an atom selected from the group consisting of nitrogen atom and sulfur atom exhibits at least one comprising a linking group.

In the general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
The fluoroalkyl group represented by C _m F _{2m + 1} may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12.
The content of such a fluoroalkyl group _{(C m F 3m + 1)} is preferably from 10 to 70 wt% with respect to the structural unit represented by formula (I), in particular 20 to 60 wt%.

R ¹ represents a single bond or a linking group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, and preferably a single bond. Examples of the linking group include —SO ₃ NR ⁴ —, —NH—, —O—, —S— and the like. Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
n shows 1-20, Preferably 2-10 is shown. l represents 0 to 10, preferably 0 to 5,

  Specific examples of the structural unit represented by the general formula (I) are given below, but the present invention is not limited to these.

The fluorine-containing surfactant in the present invention preferably contains the structural unit represented by the general formula (I) in an amount of 10% by mass to 70% by mass and preferably 20% by mass to 60% by mass of the total polymerization units. Is more preferable.
a shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100. As described above, the specific fluorine-containing surfactant can include a plurality of structural units represented by the general formula (I), but the plurality of structural units represented by the general formula (I) are the same as each other. It may be different and may contain a different thing.

(Structural unit represented by general formula (II))

In general formula (II), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other.
p shows the integer of 0-20, Preferably, it is the range of 0-10. q shows the integer of 0-20, Preferably it is the range of 0-10. r shows the integer of 0-20, Preferably, it is the range of 0-10. However, p, q, and r are not 0 at the same time.
b shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  Specific examples of the structural unit represented by the general formula (II) are listed below, but the present invention is not limited to these.

The specific fluorine-containing surfactant (F) in the present invention preferably contains 30 to 90 mol% of the structural unit represented by the general formula (II), and is 50 to 80 mol% of the total polymerization units. % Or less is more preferable.
b shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100. The specific fluorine-containing surfactant may contain two or more different structural units represented by the general formula (II).

(Other structural units)
In addition to the structural unit represented by the general formula (1) and the structural unit represented by the general formula (II), the fluorine-containing surfactant in the present invention includes other structural units (hereinafter referred to as other structural units). May be included as a copolymerization component.
The other structural unit is not particularly limited as long as it is copolymerizable with the structural unit represented by the general formula (1) and the structural unit represented by the general formula (II), and an arbitrary one is used. The

  Specific examples of other structural units include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl. Vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and the like; cycloalkyl vinyl ethers such as cyclopropyl vinyl ether, cyclobutyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether, norbornyl vinyl ether and the like; Acid vinyl esters such as vinyl acetate, propylene Vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate, etc .; α-olefins such as ethylene, propylene, isobutene, styrene, acrylonitrile, acrylamide, methacrylamide, etc. (meth) Acrylic esters, for example, methyl acrylate, methyl methacrylate (methyl acrylate and methyl methacrylate are collectively referred to as (meth) acrylate. The same applies to other examples), ethyl (meth) acrylate, propyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Rate, benzyl (meth) acrylate, phenoxy (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ) Structural units derived from monomers such as ethyl (meth) acrylate.

In addition, a structure in which part or all of the hydrogen atoms constituting the above exemplary monomer is substituted with a fluorine atom, and is not included in the structural unit represented by the general formula (I) and includes another fluorine atom Units can also be used in combination.
Among these other structural units, alkyl vinyl ethers or cycloalkyl vinyl ethers [CH ₂ ═CH (OR), wherein R represents an alkyl group or a cycloalkyl group, preferably having 1 to 12 carbon atoms. An alkyl group or a cycloalkyl group having 3 to 12 carbon atoms. ] Derived structural units are preferred.
These other structural units may use only 1 type and may use 2 or more types.

The composition of the specific fluorine group-containing surfactant according to the present invention is, as a molar ratio, a structural unit represented by the general formula (I) (a mol%): a structural unit represented by the general formula (II) (b mol) %): Other structural unit (c mol%) = 10-80: 30-90: 0-40, preferably a: b: c = 20-70: 40-90: 0-30 Is more preferable.
Moreover, the arrangement of the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and other structural units in the specific fluorine-containing surfactant is not particularly limited, and may be random. It may be regular, for example, in the form of a block or as a graft.
The mass average molecular weight of the specific fluorine group-containing surfactant is preferably 4000 to 30,000, more preferably 6000 to 25,000.
The weight average molecular weight can be measured as a value in terms of polyethylene oxide (PEO) using gel permeation chromatography (GPC).

  The specific fluorine group-containing surfactant can be synthesized by a method known in the field of polymer synthesis. Specifically, it can be performed in the presence of a radical polymerization initiator, and examples thereof include a gas phase polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method. Also, the polymerization operation can be appropriately selected according to the purpose such as batch, semi-continuous or continuous.

  Specific examples of the specific fluorine group-containing surfactant in the present invention are shown below, but the present invention is not limited to the following specific examples.

The colored curable composition for a color filter of the present invention only needs to contain at least one (F) specific fluorine-containing surfactant, and may contain two or more.
The content of the (F) specific fluorine group-containing surfactant in the colored curable composition for a color filter of the present invention is required to be 0.02 to 10% by mass, preferably 1.0 to 5. 0% by mass. When the content is in the above range, excellent coated surface properties of the colored curable composition are achieved.

[(A) Colorant]
The colored curable composition for a color filter of the present invention contains (A) a colorant. As the colorant, pigments and dyes can be used.

(Pigment)
As a pigment that can be used in the colored curable composition of the present invention, various conventionally known inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible and a handling property in consideration of handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1,7.

-Finer pigments-
In the present invention, if necessary, a fine and sized organic pigment can be used. The refinement of the pigment is a step of preparing a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salt, and grinding the pigment using the liquid composition.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol A monomethyl ether acetate etc. can be mentioned. However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  In the present invention, examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferred amount is 1 to 10 times the mass in terms of productivity, and further moisture. Is preferably 1% or less.
The amount of the water-soluble organic solvent used is in the range of 50% by mass to 300% by mass and preferably in the range of 100% by mass to 200% by mass with respect to the pigment.

  After preparing a liquid composition using each of the above components, the pigment is refined by a wet pulverizer. Here, there is no particular limitation on the operating conditions of the wet pulverizing apparatus, but in order to effectively proceed the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is that the rotational speed of the blade in the apparatus is 10 rpm to 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. In addition, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles Further, it is possible to use a coated pigment excellent in dispersion stability in which primary particles are stably maintained.

  The coated pigment, which is a preferred embodiment in the present invention, is a pigment coated with a polymer compound. However, the coating is a new interface of a highly active pigment generated by miniaturization and the side chain of the present invention. It is considered that a coating pigment having higher dispersion stability can be obtained because a strong coating layer of the polymer compound is formed by a strong electrostatic action with the polymer compound having a heterocyclic ring. That is, in the present invention, the coated polymer compound is hardly liberated even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment referred to in the present invention is characterized in that i) pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring on the side chain iv), and the polymer compound is pigment particles The effect of the present invention is achieved by firmly covering a part or all of the surface, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The pigment after the coating treatment of the present invention is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably carried out simultaneously in the pigment refinement step. Specifically, i) the pigment, ii) the water-soluble inorganic salt, and iii) a small amount of water-soluble that does not substantially dissolve ii). An organic solvent, and iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like (referred to as a salt milling step), a step of adding this mixture into water, stirring the mixture with a high speed mixer or the like, The slurry is filtered, washed with water, and dried if necessary.

The salt milling described above will be described more specifically. First, add a small amount of iii) a water-soluble organic solvent as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, knead strongly with a kneader, etc., and then throw this mixture into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
In the present invention, at the time of salt milling, by using iv) at least a partly soluble resin in combination with the above iii) organic solvent, the surface is further refined, and the surface is coated with a resin that is iv) at least partly soluble. A pigment with little aggregation of the pigment is obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling step, or may be added separately. It is also possible to add in the dispersion step.

  The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, those coated with a polymer compound having a heterocyclic ring in the side chain are preferred.

-Preparation of pigment (color matching)-
The organic pigment as the colorant can be used alone, but can be used in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments may be used alone, but at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone pigment A yellow pigment, or a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment may be mixed. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139, or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 5, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 80, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone, but a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. May be performed. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Mixture with pigment yellow 185 and pigment yellow 177 is preferable.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. If the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become larger. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a phthalocyanine pigment may be used alone, but it may be mixed with a dioxazine purple pigment. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

(dye)
In the present invention, when a dye is used as the colorant (A), a uniformly curable colored curable composition is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

(Pigment dispersion)
In the present invention, when a pigment is used as the colorant (A), it is preferable to prepare the colored curable composition of the present invention using a pigment dispersion prepared in advance.
The content of the pigment in the pigment dispersion is preferably 10% by mass to 60% by mass and more preferably 15% by mass to 50% by mass with respect to the total solid content (mass) of the composition. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

-Dispersant-
The pigment dispersion in the present invention preferably contains at least one dispersant. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc .; Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Nippon Lubrizol Corp.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content in the pigment dispersion liquid of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the mass of the above-mentioned pigment, and 3 mass%-70 mass% are more preferable.

-Pigment derivative-
A pigment derivative is added to the pigment dispersion in the present invention as necessary. By adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using this as the adsorption point of the dispersant, the pigment is made into fine particles in the pigment dispersion or colored. It can be dispersed in the curable composition to prevent reaggregation. As a result, this colored curable composition can be preferably used when forming a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. For example, JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

  As content in the pigment dispersion liquid of a pigment derivative, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

-Distribution method-
As a method for dispersing the pigment, for example, a bead disperser using a zirconia bead (for example, a disperse mat manufactured by GETZMANN), which is prepared by mixing a pigment and a dispersant and previously dispersing the mixture with a homogenizer or the like, is used. And a fine dispersion method is used.
The dispersion time is preferably about 3 to 6 hours.

[(B) Photopolymerizable compound]
The colored curable composition of the present invention contains (B) a photopolymerizable compound.
The photopolymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure, and more preferably a tetrafunctional or higher functional acrylate compound. .

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylol ethane, added with ethylene oxide and propylene oxide and then (meth) acrylated, poly (pentaerythritol or dipentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
The content of the photopolymerizable compound in the colored curable composition is preferably 5% by mass to 50% by mass, more preferably 7% by mass to 40% by mass, and more preferably 10% by mass. It is still more preferable that it is mass%-35 mass%.

[(C) Photopolymerization initiator]
The colored curable composition of the present invention contains (C) a photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050, described in US Pat. No. 4,199,420 Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in French Patent No. 2456741, coumarins or lophine dimers described in JP-A-10-62986, etc. Compound, sulfonium organoboron such as JP-A-8-015521 Body, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also use multiple types together.

  As content in the colored curable composition of a photoinitiator, 0.1 mass%-10.0 mass% are preferable with respect to the total solid of this composition, More preferably, it is 0.5 mass%. It is -5.0 mass%. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

[(D) solvent]
The colored curable composition for a color filter of the present invention contains a solvent.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; aromatic hydrocarbons such as toluene and xylene.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently. Among these, it is preferable to use a mixture of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate from the viewpoint of compatibility with the (F) specific fluorine-containing surfactant and the drying property of the film. This mixture is more preferably a mixture in which propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate are mixed in a ratio of 90:10 to 60:40.
In addition, you may use these solvents when preparing the above-mentioned pigment dispersion liquid.

[(E) Binder polymer]
The colored curable composition of the present invention contains an alkali-soluble resin as a binder polymer.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and a polymer having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. is at least one, particularly _preferably CH ^{2 = CR} 31 ^{R 32} and / or ^{_{CH 2 = C (R 31)}} (COOR 33).

  As content in the colored curable composition of alkali-soluble resin, 1 mass%-15 mass% are preferable with respect to the total solid of this composition, More preferably, they are 2 mass%-12 mass%. Especially preferably, it is 3 mass%-10 mass%.

[Optional ingredients]
The colored curable composition for a color filter of the present invention may contain various optional components depending on the purpose within a range not impairing the effects of the present invention, in addition to the components (A) to (F) described above. .
Hereinafter, optional components that can be added to the colored curable composition of the present invention will be described.
In the colored curable composition of the present invention, if necessary, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, a polymer compound other than the above alkali-soluble resin, an adhesion promoter, an oxidation agent Various additives such as an inhibitor, an ultraviolet absorber and an aggregation inhibitor can be contained.

-Thermal polymerization initiator-
It is also effective to contain a thermal polymerization initiator in the colored curable composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

-Thermal polymerization component-
It is also effective to contain a thermal polymerization component in the colored curable composition of the present invention in order to improve the film strength.
An epoxy compound is used as the thermal polymerization component. The epoxy compound is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
Specifically, for example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like (manufactured by Tohto Kasei), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101 and G102 (manufactured by Daicel Chemical) In addition, these similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Toto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei),
As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, etc.
Examples of the alicyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST. -4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

-Thermal polymerization inhibitor-
A thermal polymerization inhibitor may be added to the colored curable composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

(Preparation of colored curable composition)
The colored curable composition of the present invention comprises (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F) a specific fluorine-containing interface. In addition to the activator, it can be prepared by mixing and dispersing arbitrary components and performing a mixing and dispersing step of mixing and dispersing using various mixers and dispersers. In particular, when the colorant (A) is a pigment, it is preferable to prepare a pigment dispersion in advance and use it.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

An example of a method for preparing the colored curable composition of the present invention is shown below.
A mixture of a pigment, a water-soluble organic solvent and a water-soluble inorganic salt is mixed into a kneader such as a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder. Is used to grind the pigment while applying a strong shearing force, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, the slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a finer pigment. In addition, it is also possible to omit the process which refines | miniaturizes this pigment.

The beads are dispersed with a pigment and a dispersant and / or a pigment derivative and a solvent. Mainly using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., and finely dispersing with beads made of 0.01 mm to 1 mm particle size glass, zirconia, etc., pigment dispersion Get.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
Then, the pigment dispersion obtained as described above is subjected to (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F) a specific fluorine-containing surfactant. After adding an agent and arbitrary components, the colored curable composition for a color filter of the present invention can be obtained by passing through a mixing and dispersing step.

<Color filter and manufacturing method thereof>
The color filter of the present invention is characterized by including a colored pattern formed by the above-described colored curable composition of the present invention.
The formation of the colored pattern is preferably performed by slit coating, but it is possible to form a colored film with less defects while suppressing surface deterioration due to coating. As a result, the coloring pattern according to the present invention can be suitably applied to a pixel portion of a color filter.

Moreover, the manufacturing method of the color filter of this invention includes the process of apply | coating the colored curable composition of this invention mentioned above by the slit coating method, and forms a colored pattern on a board | substrate, It is characterized by the above-mentioned.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

As a method for producing the color filter of the present invention, first, the colored curable composition of the present invention is applied to a substrate directly or via another layer by a slit coating method suitable for coating on a large area. Perform the process. In this step, after a photocurable coating film is formed on the substrate, the coating film is exposed through a predetermined mask pattern. After exposure, the uncured portion is developed and removed with a developer to form a colored pattern. By repeating such steps, pixel portions (colored patterns) of each color (three colors or four colors) are formed on the substrate, and a color filter can be obtained.
By the above method, a color filter used for a liquid crystal display element or a solid-state image sensor can be manufactured with high quality and low cost with little difficulty in process.
Hereinafter, each process of application | coating, exposure, and image development is demonstrated.

[Coating process]
In the coating step, the colored curable composition of the present invention is coated on the substrate using a slit coating method. If an example of the slit coating method is given, first, at least one of the sides is 800 mm or longer from the slit die of the casting coating machine having a relative moving speed of 50 to 150 mm / sec with the substrate. the colored curable composition for a color filter of the invention was applied, the performed steps of forming a wet coating film having a thickness of L ¹ to the substrate surface, after which the solvent was removed by prebaking against wet film the step of forming a pre-baked coating film having a thickness of L ² Te. At this time, the film thickness L ^{1 of the} wet coating film is preferably 8 to 25 μm, and the film thickness L ² of the dry coating film is preferably 0.8 to 4.0 μm. The gap between the discharge port of the slit die and the substrate surface is in the range of 50 μm to 200 μm.
By using such a coating method using the colored curable composition of the present invention, for example, even when a fifth generation glass substrate (1100 mm × 1250 mm) is applied, a uniform coating film can be produced with high productivity. Can be formed.

Next, the board | substrate with which the colored curable composition of this invention is apply | coated is demonstrated.
As the substrate in the present invention, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film thereto, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate used in the present invention include a silicon substrate and a plastic substrate. On these substrates, usually, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, the color curable property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged. A colored pattern can be formed by the composition to produce a color filter. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate on which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate or on the surface of the driving substrate can be used.
When a colored pattern is formed on the TFT type liquid crystal driving substrate using the colored curable composition of the present invention, the photomask used for exposure has a pattern for forming pixels. In addition, it is preferable that a pattern for forming a through hole or a U-shaped depression is also provided.

After the photocurable coating film is formed as described above, a pre-bake treatment is usually performed. If necessary, vacuum treatment can be performed before pre-baking. As for the conditions for vacuum drying, the degree of vacuum is usually about 1 Pa to 300 Pa, preferably about 10 Pa to 100 Pa.
The pre-bake treatment can be performed using a hot plate, an oven or the like in a temperature range of 50 ° C. to 140 ° C. (preferably 70 ° C. to 110 ° C.) for 10 seconds to 300 seconds. Here, a high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

[Exposure process]
In the exposure step, after a photocurable coating film is formed on the substrate, the coating film is exposed through a predetermined mask pattern.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. When manufacturing a color filter for a liquid crystal display device, it is preferable that exposure using mainly h-line and i-line is performed by a proximity exposure machine and a mirror projection exposure machine.

[Development process]
In the development step, the uncured portion after exposure is eluted in the developer, leaving only the cured portion.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Moreover, as a developing solution, what melt | dissolves the coating film of the photocurable colored curable composition in an uncured part, On the other hand, as long as it does not melt | dissolve a hardening part, any thing can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

As said organic solvent, the above-mentioned solvent which can be used when preparing the pigment dispersion liquid or colored curable composition in this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001% by mass to 10% by mass, preferably 0.8%. An alkaline aqueous solution dissolved so as to be 01% by mass to 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development.
In addition, development can be performed with the substrate inclined.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and at the beginning of cleaning, used pure water is used. Sound wave irradiation can be used together.

  After the rinsing step, after draining and drying, a heat treatment is usually performed at about 200 ° C. to 250 ° C. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

  By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter in which a plurality of colored patterns (pixels) are formed can be produced.

Although the application of the colored curable composition of the present invention has been described mainly focusing on the application to a color filter, it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.
The black matrix exposes and develops the pigment dispersion in the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-bake as necessary to promote film hardening. Can be formed.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter of the present invention, is opposed to the electrode substrate, and a gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display element of the present invention. It is done.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In the following, all parts and% are based on mass unless otherwise specified.

<Synthesis example of polymer compound>
(Synthesis of polymer 1)
M-11 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Red254, CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals), 500 g of sodium chloride, 20 g of the above-described polymer 1 solution, and 100 g of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. Kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of pigment dispersion)
With a composition of Dispersic 163 (manufactured by BYK-Chemie) 7.0 parts as a dispersant and 200 parts of solvent: propylene glycol methyl ether acetate as a dispersant with respect to 35 parts of the pigment equivalent of the coated pigment 1, the number of rotations using a homogenizer Stir and mix at 3,000 rpm for 3 hours to prepare a mixed solution, and further disperse for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads. Was done.

Example 1
Components of the following composition were further added to the obtained pigment dispersion 1, and the mixture was stirred and mixed to prepare a colored curable composition for color filters (color resist solution) of the present invention. It was 3.0 cP when the viscosity (25 degreeC) of the composition was measured.
-(B) Polymerizable compound: Nippon Kayaku Co., Ltd. DPHA 20 parts-(C) Polymerization initiator: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole 3 parts. (C) Polymerization initiator: 4- [o-bromo-pN, N-di (ethoxycarbonyl)
Aminophenyl] -2,6-di (trichloromethyl) -s-
3 parts of triazine, (B) polyfunctional epoxy compound: Daikoku Ink Chemical Co., Ltd. Epiklon 695 5 parts, diethylaminobenzophenone 0.5 part, N-phenyl mercaptobenzimidazole 0.5 part, (E) alkali-soluble resin: benzyl Methacrylate and methacrylic acid (= 70/30
Copolymer with [molar ratio]) Weight average molecular weight = 30,000 20.8 parts. (F) Specific fluorine-containing surfactant: (the following compound (F-1)) 1.4 parts
(0.28 × 5)
・ (D) Solvent (propylene glycol methyl ether acetate /
400 parts ethyl 3-ethoxypropionate = 8/2)

(Coating process)
The obtained colored curable composition for a color filter is continuously fed by a pump to a slit die having a coating width of 1100 mm, and applied to a glass substrate disposed on the stage from the discharge port of the die, and the film thickness L ¹ : A 16 μm wet coating was formed. The glass substrate has a thickness of 0.7 mm and dimensions of 1100 mm × 1300 mm. The moving speed of the substrate with respect to the fixed die (relative moving speed: indicated as GSP in the table) is 100 mm / sec. The gap between the discharge port and the surface of the substrate was 150 μm. In addition, solid content in this colored curable composition was measured with the heating method. The same operation was performed in the following examples and comparative examples.
After the wet coating is formed, vacuum dry (VCD) is gently sucked for 5 seconds until the ultimate vacuum reaches 66 Pa, and is maintained for another 25 seconds after reaching the ultimate vacuum, so that the VCD TACT is 31 seconds in total. After performing under the conditions, pre-baking was performed at 110 ° C. for 80 seconds to form a pre-baked coating film (dry coating film) having a film thickness L ^{2 of} 2.42 μm.

(Evaluation of coating film)
The formed coating film was evaluated by the following method.
(1) Evaluation of Moyamura As described above, the colored curable composition was applied to a large glass substrate of 1100 mm × 1300 mm by the slit coating method, and pre-baked at 110 ° C. for 5 minutes. Irradiation with a lamp was performed to visually inspect the presence or absence of “moisture unevenness” due to unevenness on the surface of the coating film, and evaluation was performed according to the following criteria. As a result, almost no haze was observed visually and was “◯”.
A: Not visible at all.
○: Slightly visible.
Δ: Partial occurrence is observed.
X: Unevenness can be confirmed in almost all parts.

(2) Film thickness inspection The dry coating film formed by pre-baking was measured for film thickness using an a-step type needle contact measuring instrument manufactured by Tencor. As a result, the dry coating film was 2.42 μm.
(3) Coating stripe unevenness As described above, the colored curable composition was applied to a large glass substrate of 1100 mm × 1300 mm by the slit coating method, and pre-baked at 110 ° C. for 5 minutes to form a white light (UV-cut white fluorescent lamp) was irradiated, the presence or absence of “straight spot” on the surface of the coating film was visually inspected, and also confirmed by transmitted light, and evaluated according to the following criteria. As a result, almost no streak was visually observed and was “◯”.
○: No trace is observed.
Δ: A slight trace is observed but cannot be confirmed by transmission.
X: A trace is strong and a density | concentration difference can be confirmed by permeation | transmission.
(4) VCD pin unevenness Presence or absence of occurrence of film thickness unevenness (VCD pin unevenness) due to a change in the volatility of the solvent due to a temperature gradient in the contact area of the pins used when the substrate is transported from the vacuum drying process to the pre-baking process. Was visually inspected with a sodium lamp and evaluated according to the following criteria. As a result, VCD pin unevenness was hardly observed visually, and was “◯”.
A: Not confirmed at all.
○: Some can be confirmed slightly.
(Triangle | delta): It can confirm slightly on the whole and a magnitude | size is less than 5 mm.
X: It can confirm strongly and a size is also 10 mm or more.

(5) Edge bulge About the dry coating film formed by applying the photosensitive resin composition under the same conditions as described above so as to form an uncoated area of 2 mm in the coating direction. The film thickness of 10 mm was measured from the part, the maximum film thickness (swelled part film thickness) H2 in the region was measured, and the ratio (H2 / H1) between this and the central flat part film thickness H1 was calculated. It is evaluated that the smaller the edge is, the less the bulge of the end portion is, and the favorable level is 1.8.
As a result of the evaluation, it is 1.1, and it is understood that the flatness is excellent also at the end portion.

(Examples 2-15, Comparative Examples 1-4)
Each colored curable composition obtained by changing the type or amount of the specific fluorine-containing surfactant in the composition of the colored curable composition for a color filter of Example 1 to adjust the colored curable composition (resist liquid). Table 1 shows the movement speed (GSP) of the substrate with respect to the fixed die, the gap between the die discharge port and the surface of the substrate, and the vacuum dry (VCD) conditions when forming a dry coating film by an object. Other than having changed, the colored curable composition layer was formed on the board | substrate like Example 1, and it was set as Examples 2-18 and Comparative Examples 1-3.
The formed colored curable composition layer (coating film) was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Abbreviations in Table 1 are as follows.
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl 3-ethoxypropionate In Table 1, “VCD TACT” represents the time required for vacuuming to reach the degree of vacuum.

  The structures of (F-2) to (F-5) and the comparative fluorine-containing surfactant (F-C1) which are (F) specific fluorine-containing surfactants shown in Table 1 are as shown below.

  As shown in Table 1, the colored curable composition layer layer (dry coating film) formed using the colored curable composition for a color filter of the present invention has a coating defect or coating such as Moyamura, VCD pinmura, and stripe unevenness. Occurrence of the bulge at the end of the film was suppressed, and the film was uniform and excellent in flatness. On the other hand, in the colored curable composition of Comparative Example 1 that does not contain the specific fluorine-containing surfactant (F), coating defects such as stripe unevenness and moyamura due to slit coating occur, and the coating film ends rise, resulting in comparative fluorine. In the colored curable composition of Comparative Example 2 using the contained surfactant, streaks due to slit coating occurred. Further, in Comparative Example 3 in which the amount of the (F) specific fluorine-containing surfactant exceeded the range of the present invention, the substrate was easily repelled, and the occurrence of coating streaks was confirmed throughout.

<Production and Evaluation of Color Filter Substrate Having Colored Pattern>
The colored curable composition (color resist solution) prepared in each Example and Comparative Example was applied on a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) with a slit coater, and then in an oven at 90 ° C. for 60 seconds. Dried (prebaked). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the coated film after the exposure was a 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. The coating film that has been exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored resin film for forming a color filter on the glass substrate. A substrate (color filter) was produced.
In Comparative Example 3, the image streaking was not performed because the coating streaks were remarkable.
The surface state of the obtained color filter was observed with a sodium lamp and an optical microscope, and image defects (surface luminance unevenness, pinholes) were evaluated. The evaluation index is as follows.

(Image defect)
◎: No defect ○: Slightly observed but acceptable range ×: Observed and exceeded acceptable range

When the evaluation results of the image defects of the color filter obtained as described above were performed, in the coloring pattern by the colored curable composition for color filters using the (F) specific fluorine-containing surfactant in the present invention, No image defects were observed, and all were evaluated as ◎ to ○, and it was found that the occurrence of image defects that would be a practical problem was suppressed. On the other hand, in Comparative Example 1 and Comparative Example 2, image defects occurred.
From these results, it can be seen that the colored curable composition for a color filter of the present invention can form a coating film having a good surface state by suppressing the occurrence of coating defects during coating. Moreover, it turned out that the image defect of the coloring pattern after post-baking is also suppressed, and it turned out that an excellent color filter can be manufactured.

Claims (7)

(A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, (E) a binder polymer, and (F) a structural unit represented by the following general formula (I) And a colored curable composition for a color filter, containing 0.02 to 10% by mass of a surfactant containing a structural unit represented by the following general formula (II) as a copolymerization component.

In the general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other. R ¹ represents a single bond or a linking group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.
n represents an integer of 1 to 10, m represents an integer of 2 to 14, and l represents an integer of 0 to 10. a shows the mole percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
In general formula (II), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other. p is an integer of 0 to 20, q is an integer of 0 to 20, r is an integer of 0 to 20, and p, q, and r are not 0 at the same time. b shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.   The colored curable composition for a color filter according to claim 1, wherein the surfactant (F) contains 10 to 50% by mass of the structural unit represented by the general formula (I).   The colored curable composition for a color filter according to claim 1 or 2, wherein the solvent (D) is a mixture of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate.   The colored curable composition for a color filter according to any one of claims 1 to 3, wherein the colorant (A) is a pigment coated with a resin.   The color filter which has a coloring pattern formed with the coloring curable composition for color filters of any one of Claims 1-4 on a board | substrate.   The manufacturing method of the color filter which has the coloring pattern formation process including the process of apply | coating the coloring curable composition for color filters of any one of Claim 1 to 4 with a slit coating method on a board | substrate.   A crystal display device comprising a color filter obtained by the method for producing a color filter according to claim 6.