JP2009098193A - Coloring curable composition, colored pattern, color filter and method of manufacturing the same, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring curable composition from which a colored pattern with high definition having a rectangular or normally tapered cross-sectional form and excellent adhesiveness to a solid surface can be formed by exposure and development. <P>SOLUTION: The coloring curable composition includes (a) a colorant, (b) a polymerizable compound having an ethylenically unsaturated double bond, (c) a photopolymerization initiator, (d) a compound in which a polymerization inhibition moiety and a surface orientation moiety are connected, and (e) a solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a colored pattern formed using the colored curable composition, a color filter having the colored pattern, a production method thereof, and a liquid crystal display element.

  The color filter contains a pigment dispersion liquid in which organic pigments and inorganic pigments are dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored curable composition, which is used for photolithography. It is manufactured by forming a colored pattern or a black matrix.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. In addition, color filters for image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction of color unevenness and improvement of color resolution, and high definition is also desired. ing.

  As described above, in recent years, the demand for high color reproducibility of color filters is increasing, and colored curable compositions tend to have high pigment concentrations. However, when a colored pattern is formed by a photolithography method using a colored curable composition with a high pigment concentration, the pigment is hindered or absorbed by ultraviolet rays, so that the exposure is insufficient. There is a tendency that the deep part curability is not obtained. As a result, there is a problem that undercut is likely to occur in the development process, and adhesion to the substrate is poor.

  In addition, when forming a colored pattern by photolithography, if the exposure dose of ultraviolet irradiation is increased in order to develop deep curability, the line width of the surface portion (upper part) of the pattern cross section becomes wider than the exposure region, and the deepest There is a problem that an undercut occurs due to an increase in the line width of the portion (low portion). Thus, when the shape of the colored pattern is an undercut shape, after the color filter is produced, the pattern is peeled off, and problems such as disconnection of the ITO electrode deposited on the upper layer are not preferable. Further, since the line width of the surface portion is wider than the exposure region, there is a problem that it becomes difficult to obtain a high-definition colored pattern.

Conventionally, several techniques for suppressing the occurrence of such an undercut shape have been proposed. For example, a technique for forming a rectangular or forward taper after development by adding a chain transfer agent to the photosensitive composition is disclosed (for example, see Patent Document 1).
As another proposal, a technique for forming a forward taper by including a copolymer having an imide group and an epoxy group in the photosensitive composition is disclosed. (For example, see Patent Document 2.)

However, with the above two techniques, for example, when forming a colored pattern having a pigment concentration of 30% or more, it is difficult to form a pattern having a high definition and a rectangular or forward tapered shape after the development process. .
That is, for example, in a film thickness of about 2.0 μm, there is a demand for a colored curable composition that can provide a sufficient surface curability and deep part curability upon exposure and can form a colored pattern with excellent pattern formability. is the current situation.
JP 2002-167404 A JP 2004-341245 A

That is, 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 having a high-definition, rectangular or forward-tapered cross-sectional shape by exposure and development, and capable of forming a colored pattern having excellent adhesion to a solid surface. It is to provide.
Another object of the present invention is a high-definition, rectangular or forward-tapered cross-sectional shape, a colored pattern having excellent adhesion to a solid surface, a color filter having the colored pattern, a method for producing the same, And providing a liquid crystal display device including the color filter.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
That is, the colored curable composition of the present invention comprises (a) a colorant, (b) a polymerizable compound having an ethylenically unsaturated double bond, (c) a photopolymerization initiator, (d) a polymerization inhibition site and a surface. It contains a compound formed by linking an alignment site, and (e) a solvent.

  In the present invention, (d) a compound formed by linking a polymerization inhibition site and a surface alignment site includes a unit skeleton having a phenol group represented by the following general formula (1) and a unit skeleton having a fluoro group. A copolymer is preferred.

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent.

  The unit skeleton having a phenol group represented by the general formula (1) is preferably a unit skeleton represented by the following general formula (2), general formula (3), or general formula (4).

In the general formulas (2) to (4), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent, and R ⁵ represents a hydrogen atom or a methyl group. , R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X and Y each independently represent an alkylene group having 1 to 6 carbon atoms.

  The unit skeleton having a fluoro group is preferably a unit skeleton having a group represented by the following general formula (5).

  In said general formula (5), n represents the arbitrary integers of 1-20.

  The unit skeleton having a fluoro group is preferably a unit skeleton represented by the following general formula (6).

In the general formula (6), R ⁷ represents a hydrogen atom or a methyl group, Z is an alkylene group having 1 to 6 carbon atoms, n represents represents any integer from 1 to 20.

  In the colored curable composition of the present invention, it is preferable that the content of (a) the colorant is 20% or more and 60% or less in terms of mass fraction with respect to the total solid content of the colored curable composition.

The colored pattern of the present invention is formed by the colored curable composition of the present invention.
The color filter of the present invention is characterized by having the colored pattern of the present invention on a substrate.
Furthermore, the color filter of the present invention is characterized in that an arbitrary colored pattern is formed on a substrate by repeating the coating, prebaking, exposure, and development using the colored curable composition of the present invention.
In addition, the liquid crystal display device of the present invention is equipped with the color filter of the present invention.

The compound formed by linking (d) the polymerization prohibition site and the surface alignment site used in the present invention, when the coating film is formed with the colored curable composition of the present invention due to the presence of the surface alignment site, It is a compound that is unevenly distributed on the surface. Moreover, this (d) component has a function which stops the radical photopolymerization reaction which generate | occur | produced by exposure by having a polymerization prohibition site | part. Due to these points, when a coating film is formed using the colored curable composition of the present invention containing the component (d), first, the component (d) is unevenly distributed only near the surface, and the coating film is exposed. (C) When radicals are generated from the photopolymerization initiator, the polymerization-inhibited sites in the component (d) function only on the film surface and a polymerization termination reaction occurs. That is, it can suppress that a polymerization reaction is accelerated only by the coating-film surface. By these operations, when the colored curable composition of the present invention is exposed to light and developed to form a colored pattern, an appropriate polymerization inhibiting effect is exerted on the surface of the coating film. Since the difference in curability with the deep part of the film becomes small and the hardened area can be prevented from spreading on the surface more than the exposed area, the coloring pattern has a high-definition and rectangular or forward taper cross-sectional shape. Can be formed.
In particular, the use of the component (d) having a phenolic hydroxyl group improves the solubility of the developer in the unexposed area, which is more preferable for obtaining the effects of the present invention.

According to the present invention, there is provided a colored curable composition having a high-definition, rectangular or forward-tapered cross-sectional shape by exposure and development, and capable of forming a colored pattern having excellent adhesion to a solid surface. Can be provided.
According to the present invention, a colored pattern having a high-definition and rectangular or forward-tapered cross-sectional shape and having excellent adhesion to a solid surface, a color filter having the colored pattern, a production method thereof, and the A liquid crystal display device including a color filter can be provided.

Hereinafter, the present invention will be described in detail.
<Colored curable composition>
The colored curable composition of the present invention comprises (a) a colorant, (b) a polymerizable compound having an ethylenically unsaturated double bond, (c) a photopolymerization initiator, (d) a polymerization inhibition site and a surface orientation site. And (e) a solvent, and a solvent.
Hereinafter, the components (a) to (e) will be described.

[(A) Colorant]
The colored curable composition of the present invention contains (a) a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the colored curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of light resistance.

-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 particle diameter of 0.01 to 0.3 μm, more preferably 0.01 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.

  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 4,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,

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

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of such combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture of an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, and the like can be used. 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. A mixture with CI 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.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment or a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. be able to. 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. A mixture of CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, when the ratio exceeds 100: 200, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. 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 purple pigment is preferably 100: 0 to 100: 50, and more preferably 100: 30 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.

In the present invention, a fine and sized organic pigment can be used as necessary.
In order to refine the organic pigment, it is preferable to use a method including a step of grinding the organic pigment as a highly viscous liquid composition together with the water-soluble organic solvent and the water-soluble inorganic salts.
In the present invention, it is more preferable to use the following method for refining the organic pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single The organic pigment in the mixture is ground by applying a strong shearing force using a kneader such as a twin or twin screw extruder, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a refined organic pigment.

Examples of the water-soluble organic solvent used in the above-mentioned refinement method include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoester. Examples include butyl ether, propylene glycol, and propylene glycolic monomethyl ether acetate.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in 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. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the organic pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The amount of the water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferred amount is 1 to 10 times the mass. is there.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when a liquid composition containing an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is ground, a wet grinding device such as the kneader described above may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, 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 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, Organic pigments can be obtained.

-Dye-
In the present invention, when a dye is used as the colorant, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the colored curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters 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 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder polymer and / or the dye in the non-irradiated part by development. .
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto.
For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83 , 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3 , 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17 , 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 , 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and the like and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

  Among them, as colorants, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo A colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferred.

The colorant that can be used in the present invention is a dye or a pigment having an average particle diameter r (unit: nm) satisfying 5 ≦ r ≦ 250, preferably 10 ≦ r ≦ 200, particularly preferably 15 ≦ r ≦ 150. desirable. By using a pigment having such an average particle diameter r, a colored pixel having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture liquid prepared can be prepared, for example, by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

-Pigment dispersion-
The pigment dispersion containing the above pigment is obtained by dispersing (a) a pigment as a colorant in a solvent together with a dispersant and a pigment derivative.
The dispersant used here is used for improving the dispersibility of the pigment. For example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used as the dispersant. 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.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene 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 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical 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.

In addition, a pigment derivative is added to the pigment dispersion in the present invention as necessary.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is dispersed as fine particles. It can be dispersed in the liquid, and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the dispersant by modifying the pigment surface.

  Specifically, the pigment derivative used in the present invention 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 as a substituent in the side chain. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, Examples include imidazolone pigments. 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. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion liquid of the pigment derivative based on this invention, 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.

Examples of the solvent constituting the pigment dispersion in the present invention include the same as the solvent (e) described later.
The pigment concentration in the pigment dispersion is preferably 30% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass.

The pigment dispersion in the present invention can be prepared through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, for example, a bead disperser using zirconia beads or the like (for example, manufactured by GETZMANN Co., Ltd.) is prepared by previously mixing a pigment and a dispersant as necessary, and further dispersing in advance with a homogenizer or the like. The pigment dispersion liquid can be prepared by finely dispersing using a disperse mat).
The dispersion time is preferably about 3 to 6 hours.
In addition, fine dispersion treatment with beads mainly includes vertical or horizontal sand grinders, pin mills, slit mills, ultrasonic dispersers, etc., and beads made of glass having a particle diameter of 0.01 to 1 mm, zirconia, or the like. Can be used.
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.

The content of the colorant in the colored curable composition is preferably 20% by mass to 60% by mass and more preferably 30% by mass to 55% by mass with respect to the total solid content of the composition. .
When the concentration of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.

[(B) Polymerizable compound having an ethylenically unsaturated double bond]
The colored curable composition of the present invention contains (b) a polymerizable compound having an ethylenically unsaturated double bond (hereinafter simply referred to as “polymerizable compound”).
Examples of the polymerizable compound in the present invention include polymerizable monomers or oligomers having one or more ethylenically unsaturated double bonds. Among them, one or more ethylenically unsaturated double bonds have a boiling point. A compound that is 100 ° C. or higher at normal pressure is preferred.

Examples of the compound having at least one ethylenically unsaturated double bond and having a boiling point of 100 ° C. or higher at normal pressure include, for example, 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) ether Tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and (meth) acrylate after addition of ethylene oxide or propylene oxide, poly (meth) of pentaerythritol or dipentaerythritol Acrylates, 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 and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, can be mentioned in JP-A 52-30490.
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.

The polymerizable compound in the present invention can be used in combination of two or more, in addition to being used alone.
As content in the coloring curable composition of a polymeric compound, 2 mass%-30 mass% are preferable with respect to the total solid of this composition, More preferably, they are 3 mass%-25 mass%, Especially preferably, it is 5 mass%-20 mass%. When the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.

[(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 each specification such as US Pat. No. 4,318,791 and European Patent No. 88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic ketone compounds such as, compounds of (thio) xanthones or acridines described in French Patent No. 2456741, compounds such as coumarins or lophine dimers described in JP-A-10-62986, and the like Sulfonium organoboron complex etc. disclosed in Kaihei 8-015521 etc. It can gel.

  In the present invention, the photopolymerization initiator includes acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarin, biimidazole, oxime. An ester type or the like is 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.

  Preferable examples of the acridine 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 biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  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 of the photopolymerization initiator in the present invention include carbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds 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, the 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 thereof include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the colored curable composition of a photoinitiator, 0.1 mass%-15.0 mass% are preferable with respect to the total solid of this composition, More preferably, 0.3 mass% It is -10.0 mass%, Most preferably, it is 0.5 mass%-8.0 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) Compound formed by linking polymerization-inhibited site and surface orientation site]
The colored curable composition of the present invention contains a compound in which a polymerization inhibition site and a surface orientation site are linked (hereinafter, referred to as “specifically linked compound” as appropriate).
The specific linking compound in the present invention may be a low molecular compound or a high molecular compound as long as it has a polymerization inhibition site and a surface orientation site in the molecule, and these two sites are linked. However, from the viewpoint of film surface orientation of the specific linking compound, sublimation of the specific linking compound during pre-baking, and prevention of diffusion, a polymer compound is preferable.

The polymerization inhibition site in the present invention is not particularly limited as long as it is a structure derived from a compound having a known polymerization inhibition ability (polymerization inhibitor). Specifically, a phenol-based inhibitor, an amine-based inhibitor, Sulfur-based inhibitors, phosphorus-based inhibitors and the like can be mentioned.
Of these, phenol-based inhibitors are preferred from the viewpoint of polymerization inhibition ability, solubility in an alkaline developer, and developability.

In addition, the surface orientation site in the present invention is not particularly limited as long as it is a site having the property of being oriented on the surface in the composition, and specifically, a fluorine compound, a silicon compound, a hydrocarbon compound, etc. Is mentioned.
Among these, a fluorine-based compound is preferable from the viewpoint of surface orientation.

In the specific linking compound of the present invention, the linking group for linking the polymerization inhibition site and the surface orientation site is not particularly limited. Examples of the linking group include an alkylene group, an alkenylene group, an arylene group, -O-. , —S—, —CO—, —NR′— (R ′ represents a hydrogen atom, an alkyl group, or an aryl group), or a linking group formed by combining two or more of these. Especially, the aspect which is a high molecular compound which a polymerization prohibition site | part and a surface orientation site | part each have in a side chain is preferable.
The content of the polymerization prohibited site and the surface orientation site in one molecule of the specific linking compound is not particularly limited as long as both functions can be expressed, but the content of the polymerization prohibited site and the surface orientation site is not limited. A specific linking compound having a molar ratio of about 1: 1 is preferred.

Hereinafter, the preferable aspect of the specific connection compound in this invention is demonstrated.
The specific linking compound in the present invention is preferably a phenol group-containing copolymer.
The phenol group-containing copolymer used in the present invention is preferably a copolymer containing at least a unit skeleton having a phenol group represented by the following general formula (1) and a unit skeleton having a fluoro group. .

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent.
When R ¹ , R ² , R ³ , and R ⁴ are substituents, examples of the substituent include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, halogen atoms, amino groups, and substituents. Amino group, carboxylic acid group, substituted carbonyl tomb, hydroxyl group, silyl group, nitro group, cyano group, alkenyl group, alkynyl group, aryl group, heterocyclic group, sulfo group, substituted sulfonyl group, sulfonate group, substituted sulfinyl group, phosphono Group, substituted phosphono group, phosphonato group, substituted phosphonato group and the like. Among these, a methyl group, a methoxy group, and an amino group are preferable from the viewpoint of polymerization inhibiting ability.

  Examples of the phenol group represented by the general formula (1) include the following structures (1a) to (1c).

The structure of the main chain in the unit skeleton having a phenol group represented by the general formula (1) is not particularly limited, and examples thereof include a hydrocarbon chain, a polyester chain, a polyether chain, a polyamide chain, and a polythioether chain.
Further, the main chain and the phenol group represented by the general formula (1) may be directly bonded or may be bonded via a linking group.
As a linking group, an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group or an aryl group), or two or more thereof Examples thereof include a linking group formed in combination.

  Among these, from the viewpoint of polymerization inhibition ability and developability, the unit skeleton having a phenol group represented by the general formula (1) is represented by the following general formula (2), general formula (3), or general formula (4). It is preferable that it is a unit skeleton.

In the general formulas (2) to (4), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent, and R ⁵ represents a hydrogen atom or a methyl group. , R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X and Y each independently represent an alkylene group having 1 to 6 carbon atoms.

For ^{R 1,} R 2, ^{R 3,} and ^{R 4} in the general formula (2) to the general formula (4), ^{R 1,} R 2, ^{R 3} in Formula (1), and has the same meaning as ^{R 4} The preferred examples are also the same.
When R ⁶ in the general formula (4) is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Furthermore, as a C1-C6 alkylene group represented by X and Y in General formula (4), a methylene group, ethylene group, a propylene group, a butylene group, etc. are mentioned specifically, Among these, a methylene group , Ethylene group and propylene group are preferred.
Among the unit skeletons represented by the general formula (2) to the general formula (4), the unit skeleton represented by the general formula (2) or the general formula (3) from the viewpoint of polymerization inhibition ability, sensitivity, and developability. Is preferred.

  Hereinafter, although the specific example of the unit frame | skeleton which has a phenol group represented by General formula (1) is shown, this invention is not limited to these.

  The unit skeleton having a phenol group represented by the general formula (1) described above contributes to the polymerization termination reaction in the exposed region and to the solubility in an alkali developer in the unexposed region. Therefore, the content ratio of the unit skeleton in the phenol group-containing copolymer may be adjusted in consideration of sensitivity, solubility, balance with the unit skeleton having a fluoro group, and other physical properties. The range is preferably from mol% to 90 mol%, more preferably from 40 mol% to 80 mol%, and still more preferably from 50 mol% to 70 mol%.

  On the other hand, in the phenol group-containing copolymer used in the present invention, the unit skeleton having a fluoro group is preferably a group represented by the following general formula (5).

In said general formula (5), n represents the arbitrary integers of 1-20. Especially, in order to fully exhibit the surface orientation performance, n is preferably an integer of 3 to 20, and n is more preferably an integer of 6 to 12.
The structure of the main chain in the unit skeleton having the group represented by the general formula (5) is not particularly limited, and examples thereof include a hydrocarbon chain, a polyester chain, a polyether chain, a polyamide chain, and a polythioether chain.
Further, the main chain and the group represented by the general formula (5) may be bonded directly or via a linking group.
As the linking group, an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group, or an aryl group), or two of these Examples thereof include a linking group obtained by combining the above.

  In addition, the unit skeleton having a fluoro group has the following general formula (from the viewpoint of sensitivity, surface orientation performance, solubility in an alkaline developer in an unexposed region, and adhesion to the solid surface of the formed film. The unit skeleton represented by 6) is more preferable.

In the general formula (6), R ⁷ represents a hydrogen atom or a methyl group, Z is an alkylene group having 1 to 6 carbon atoms, n represents represents any integer from 1 to 20.
Here, n in General formula (6) is synonymous with n in the said General formula (5), and its preferable example is also the same.
Furthermore, specific examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the general formula (6) include a methylene group, an ethylene group, a propylene group, and a butylene group. Group and propylene group are preferred.

  Specific examples of the unit skeleton having a fluoro group are shown below, but the present invention is not limited thereto.

  The unit skeleton having a fluoro group described above contributes to make the phenol group-containing copolymer unevenly distributed on the coating film surface. Therefore, the content ratio of the unit skeleton in the phenol group-containing copolymer may be adjusted in consideration of whether or not the surface alignment performance is expressed, and is, for example, in the range of 20 mol% to 60 mol%. Is more preferable, it is more preferably in the range of 25 mol% to 55 mol%, and still more preferably in the range of 30 mol% to 50 mol%.

Furthermore, the phenol group-containing copolymer in the present invention may further have another unit skeleton in the molecule. The other unit skeleton is preferably a unit skeleton having a group that promotes alkali solubility.
That is, when a phenol group-containing copolymer containing a unit skeleton having a group that promotes alkali solubility is used in the colored curable composition of the present invention, pattern formation occurs when the colored curable composition is exposed and developed. In addition to improving the properties, there is an effect of further improving the solubility of the unexposed portion in the alkaline developer.

  Here, examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Further, the group that promotes alkali solubility may be contained in the unit skeleton having a phenol group represented by the general formula (1) or in the unit skeleton having a fluoro group.

  The unit skeleton having a group that promotes alkali solubility in the present invention is preferably a unit skeleton represented by the following general formula (8).

In the general formula (8), R ⁸ represents a hydrogen atom or a methyl group.

The phenol group-containing copolymer in the present invention may further contain a unit skeleton having an ester group in the molecule as another unit skeleton. A phenol group-containing copolymer including a unit skeleton having an ester group is preferable from the viewpoint of adjusting sensitivity and compatibility with a solvent and a binder polymer.
The unit skeleton having an ester group is preferably a unit skeleton represented by the following general formula (9).

In the general formula (9), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an alkyl group or an aralkyl group.
Examples of the alkyl group represented by R ¹⁰ include an alkyl group having 1 to 13 carbon atoms, and examples of the aralkyl group represented by R ¹⁰ include aralkyl groups such as a benzyl group and a phenylethyl group. .

The skeleton unit represented by the general formula (9) is preferably derived from the following monomers.
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Examples thereof include phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate and the like. Among them, a skeleton unit derived from methyl (meth) acrylate and benzyl (meth) acrylate is preferable from the viewpoint of sensitivity and compatibility with a solvent and a binder polymer.

  Specific examples of the specific linking compound in the present invention [phenol group-containing copolymers (1) to (4)] are shown below, but the present invention is not limited thereto.

A synthesis example of the phenol group-containing copolymer (3) of the present invention having the above structure is as follows.
In a 200 ml flask, 10.58 g (0.06 mol) of t-butoxystyrene, 12.94 g (0.03 mol) of perfluorohexylethyl methacrylate, and 0.86 g (0.01 mol) of methacrylic acid were added to 40 ml of tetrahydrofuran. It melt | dissolved, 1.0g of polymerization initiator V-601 (made by Wako Pure Chemical Industries Ltd.) was added under nitrogen stream and stirring, and reaction was performed at 70 degreeC for 3 hours. After allowing the reaction solution to cool, hexane was added while stirring to precipitate the resin. The obtained resin was washed with hexane and dried under reduced pressure. Subsequently, 20 g of the resin obtained in a 200 ml flask was weighed, 200 g of propylene glycol monomethyl ether and 20 ml of concentrated hydrochloric acid were added, and the reaction was performed at 80 ° C. for 3 hours. After allowing the reaction solution to cool, ion-exchanged water was added while stirring to precipitate a white resin. The obtained resin was washed with ion-exchanged water and dried under reduced pressure to obtain a phenol group-containing copolymer of the present invention. When the molecular weight was measured by GPC, the weight average (Mw: polystyrene conversion) was 10,000.

  The molecular weight of the phenol group-containing copolymer in the present invention is preferably in the range of 3,000 to 200,000 as a weight average molecular weight, preferably 4,000 to 100,000, and more preferably 5,000 to 50,000. 000.

  The (d) specific linking compound in the present invention is preferably blended at a mass fraction of 0.1% to 10.0% with respect to the total solid content of the colored curable composition. More preferably, it is 0.3% or more and 8.0% or less, More preferably, it is 0.5% or more and 5.0% or less. When the amount of the specific linking compound used is small, it is difficult to form a rectangular or forward tapered cross-sectional shape, and it is difficult to obtain a high-definition colored pattern. Further, when the amount used is large, the development latitude becomes narrow, and the adhesion of the formed colored pattern to the solid surface also decreases.

[(E) Solvent]
In general, the colored curable composition of the present invention can be suitably prepared by using (e) a solvent together with the above components.
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, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropio Acid 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, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, 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, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

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 it independently.

[Other ingredients]
The colored curable composition of the present invention is filled with a binder polymer, a sensitizing dye, a hydrogen-donating compound, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, and the like as necessary. Various additives such as an agent, a polymer compound other than the alkali-soluble resin (binder polymer), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent can be contained.

-Binder polymer-
The colored curable composition of the present invention preferably contains a binder polymer.
The binder polymer is a linear organic polymer, and is a group that 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 suitably selected from alkali-soluble resins having (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, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
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.

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 acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

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 ¹ R ² , CH ² = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

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

-Sensitizing dye-
A sensitizing dye may be added to the colored curable composition of the present invention as necessary. The sensitizing dye can promote the radical generation reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently (It can be a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ¹ ) —, and Y represents an oxygen atom. Or -N (R ¹ )-, wherein R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A and R ¹ , R ² , R ³ and Can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ¹ , R ² , and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂₎ and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Rubonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, Methyl Phosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² and R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of the substituted aryl group that is preferable as R ¹ , R ² , and R ³ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aforementioned aryl group. What you have is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. Also, as more preferred examples of R ¹ include substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A in the general formula (XVIII) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ¹ and R ² in the general formula (XVIII). , Or the same as those exemplified in the above description of R ³ .
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the formula (XVIII) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7,6,4,5-thiazoles (eg 4-methoxythianaphtheno-7,6,4,5-thiazole etc.), oxazoles (eg 4-methyl Oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxyben Zooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

  Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  Of the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y in cooperation with the above-mentioned A and the adjacent carbon atom in the general formula (XVIII) described above, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-31253 as a novel compound.

(In General Formula (XVIII-2), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -N (R ¹ )-. R ¹ , R ⁴ , R ⁵ , R ⁶ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ , R ⁵ , R ⁶ are bonded to each other, An aromatic or aromatic ring can be formed.)
In formula (XVIII-2), A and ^{R 1} are the same as in the general formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) And R ⁶ has the same meaning as R ¹ in formula (XVIII).

  Next, the compound represented by formula (XVIII-3), which is a preferred embodiment of the compound represented by formula (XVIII) used in the present invention, will be described.

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ¹ ) —. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ and R ⁵ are each aliphatic or aromatic. Can be linked to form a ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In formula (XVIII-3), A and ^{R 1} have the same meanings as in formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) It is synonymous with.
Moreover, Ar in the general formula (XVIII-3) represents an aromatic ring or a hetero ring having a substituent, and as specific examples, among those previously described in the description of A in the general formula (XVIII), Specific examples relating to the aromatic ring or heterocyclic ring having a substituent are also included. However, as a substituent that can be introduced into Ar in the general formula (XVIII-3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples thereof include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary Compound (F1) to Illustrative Compound (F56)] are shown below, but the present invention is not limited to these. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep part curability.

  The above sensitizing dye can be subjected to various chemical modifications as follows for the purpose of improving the characteristics of the colored curable composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1% with respect to the total solid content of the colored curable composition. ˜5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

-Hydrogen donating compound-
The colored curable composition of the present invention preferably contains a hydrogen donating compound. In the present invention, the hydrogen-donating compound has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such hydrogen donating compounds include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of the hydrogen donating compound include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142277, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Further examples of the hydrogen donating compound include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B-55. -34414, a hydrogen donor described in JP-A-6-308727, and a sulfur compound (eg, trithiane).

  The content of these hydrogen-donating compounds is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the colored curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Is preferable, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

-Fluorine organic compounds-
The colored curable composition of the present invention can also contain a fluorine-based organic compound.
By containing this fluorinated organic compound, the liquid properties (particularly fluidity) when the colored curable composition of the present invention is used as a coating liquid can be improved, and the uniformity of coating thickness and liquid-saving properties can be improved. Can be improved. That is, since the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coating property to the surface to be coated is improved. Even when a thin film is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

  As described above, the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Furthermore, it is also effective when applied to slit coating that easily causes liquid breakage.

  0.001-2.0 mass% is preferable with respect to the total mass of a colored curable composition, and, as for the addition amount of a fluorine-type organic compound, More preferably, it is 0.005-1.0 mass%.

-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-
In order to increase the strength of the film, it is also effective to contain a thermal polymerization component in the colored curable composition of the present invention. As the thermal polymerization component, an epoxy compound is preferable.
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.
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 ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  The cresol novolak type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type As alicyclic epoxy compounds, such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302 , GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto 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 In addition to diglycidyl ester, amine-type epoxy resins such as Epototo YH-434 and YH-434L, glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resin, and the like can also be used.

-Surfactant-
The colored curable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coating properties, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  Moreover, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, Nonionic surfactants such as 150R1 and anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) can also be used.

-Other additives-
In addition to the above, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, Alkali-soluble resins such as those obtained by adding an acid anhydride to a polymer having a hydroxyl group, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA High polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Molecular dispersant; Solsperse 3000 Various Solsperse dispersants such as 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95 , F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.); 2- (3-t- UV absorbers such as butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

Further, when the alkali solubility of the uncured part is promoted and the developability of the colored curable composition is further improved, the colored curable composition may have an organic carboxylic acid, preferably a low molecular weight of 1000 or less. It is preferable to add an organic carboxylic acid.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, Aromatic polymers such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid Rubonic acid; Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

-Thermal polymerization inhibitor-
In addition to the above, a thermal polymerization inhibitor can also 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 this invention contains the above-mentioned (a)-(d), and can be further prepared by mixing additives, such as surfactant, as needed.
In the case where (a) the colorant is a pigment, first, a pigment dispersion may be prepared as described above, and then the colored curable composition of the present invention may be obtained using this pigment dispersion.
When the pigment dispersion is used for preparing the colored curable composition of the present invention, the content of the pigment is 20% by mass or more and 60% by mass with respect to the total solid content (mass) of the colored curable composition. The amount in the range of not more than mass% is preferable, and the amount in which the pigment content is in the range of not less than 30 mass% and not more than 55 mass% is more preferable.
When the content of the pigment dispersion is within this range, the color density is sufficient and effective in securing excellent color characteristics.

In the colored photocurable composition of the present invention, (d) due to the presence of the specific linking compound, a rectangular or forward tapered cross-sectional shape is formed after the exposure / development process, and a high-definition and high-hardness colored pattern is formed. be able to.
Therefore, it is preferably used for forming a colored pattern of a color filter that requires a good cross-sectional shape.

<Coloring pattern, color filter, and manufacturing method thereof>
The colored pattern of the present invention is formed by the above-described colored curable composition of the present invention.
The obtained colored pattern has a rectangular or forward-tapered cross-sectional shape and is a high-definition and high-hardness colored pattern, and thus can be applied to a pixel portion of a color filter or the like.

The color filter of the present invention has a colored pattern formed on the substrate by the above-described colored curable composition of the present invention.
Moreover, the manufacturing method of the color filter of this invention uses the above-mentioned colored curable composition of this invention, and forms arbitrary colored patterns by repeating application | coating, prebaking, exposure, and image development.
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 described above, the method for producing a color filter of the present invention includes the steps of coating, pre-baking, exposure, and development. By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, 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, 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 disposed is used. In addition, a color filter formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, 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 in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the colored curable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored curable composition from the slit nozzle is usually 500 to 2000 microliters / second, preferably 800 to 1500 microliters / second, and the coating speed is usually 50 to 300 mm. / Sec, preferably 100 to 200 mm / sec.
Moreover, as solid content of the colored curable composition used at an application | coating process, it is 10-20% normally, Preferably it is 13-18%.

When forming a coating film with the colored curable composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 4 0.0 μm, most preferably 0.5 to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
As the conditions for vacuum drying, the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. High frequency processing can be used alone.

[Exposure process]
In the exposure step, the coating film made of the colored curable composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

[Development process]
In the development step, the uncured portion of the coated film after exposure is eluted into the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the colored curable composition in the uncured part while not dissolving the cured part.
Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 An alkaline aqueous solution dissolved so as to be ˜1 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. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development processing, the substrate is dried through a rinsing process for washing and removing excess developer.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After drying as described above, heat treatment at 100 ° C. to 250 ° C. is usually performed.
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.
Such post-baking is a process for the purpose of complete curing and for the purpose of forward-tapering the pattern shape after development by thermal deformation, and heating (hard baking) at 200 ° C. to 250 ° C. It is common to do.
Since the colored curable composition of the present invention has a good cross-sectional shape and can form a film with high hardness, it has a sufficient hardness and cross-sectional shape as a color filter after rinsing and drying. The post-baking in the color filter manufacturing process can be omitted.

  By repeating the above steps in order for each color according to the desired number of hues, a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed can be produced.

As the application of the colored curable composition of the present invention, the description has mainly focused on the application to the color pattern of the color filter, but also for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

<Liquid crystal display device>
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 the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display device of the present invention. It is done.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(1. Preparation of colored curable composition)
Example 1
Blue pigment C.I. I. 200 parts of Pigment Blue 15: 6, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a blue pigment were obtained.
The purple pigment C.I. I. 200 parts of Pigment Violet 23, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a violet pigment were obtained.

  The pigment refined as described above was used, and the rotational speed was 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution.

〔composition〕
Pigment Blue 15: 6 (average primary particle diameter 25 nm) 90 parts Pigment Violet 23 (average primary particle diameter 25 nm) 10 parts Phthalocyanine derivative (manufactured by Solsperse 3000) 10 parts benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 5,000) in propylene glycol monomethyl ether acetate solution (solid content 40%) ... 75 parts Dispersant (BYK-161, manufactured by BYK) ... 35 Parts ・ Propylene glycol monomethyl ether acetate… 495 parts

  Subsequently, the mixed solution obtained above was further subjected to co-dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads.

  Components of the following composition were further added to the obtained pigment dispersion, and the mixture was stirred and mixed to prepare the colored curable composition 1 (color resist solution) of the present invention. In addition, the pigment density | concentration in the total solid of the obtained colored curable composition 1 was 48%.

〔composition〕
Dipentaerythritol hexaacrylate 30 parts 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 10 parts (photopolymerization initiator)
・ 4,4′-bis (diethylamino) benzophenone (sensitizing dye) 5 parts ・ 2-mercaptobenzothiazole (hydrogen donating compound) 5 parts ・ The following (d1) phenol group-containing copolymer (weight average molecular weight) 10,000) 5 parts propylene glycol monomethyl ether acetate 230 parts

(Example 2)
Green pigment C.I. I. 200 parts of Pigment Green 36, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a green pigment were obtained.
The yellow pigment C.I. I. 200 parts of Pigment Yellow 150, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a violet pigment were obtained.

  The pigment refined as described above was used, and the rotational speed was 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution.

〔composition〕
Pigment Green 36 (average primary particle diameter 25 nm) 70 parts Pigment Yellow 150 (average primary particle diameter 25 nm) 30 parts Phthalocyanine derivative (manufactured by Solsperse 3000) 10 parts benzyl methacrylate / methacrylic acid (= 70 / 30 [molar ratio]) copolymer (weight average molecular weight: 5,000) in propylene glycol monomethyl ether acetate solution (solid content 40%) 75 parts, dispersant (BYK-161, manufactured by BYK) 35 parts Propylene glycol monomethyl ether acetate 495 parts

  Subsequently, the mixed solution obtained above was further subjected to co-dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads.

  Components of the following composition were further added to the obtained pigment dispersion and mixed by stirring to prepare a colored curable composition 2 (color resist solution) of the present invention. In addition, the pigment concentration in the total solid content of the obtained colored curable composition 2 was 48%.

〔composition〕
Dipentaerythritol hexaacrylate 30 parts 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 10 parts (photopolymerization initiator)
・ 4,4′-bis (diethylamino) benzophenone (sensitizing dye) 5 parts ・ 2-mercaptobenzothiazole (hydrogen-donating compound) 5 parts ・ The above (d1) phenol group-containing copolymer (weight average molecular weight) 10,000) 5 parts propylene glycol monomethyl ether acetate 230 parts

(Example 3)
Green pigment C.I. I. 200 parts of Pigment Red 254, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a green pigment were obtained.
The yellow pigment C.I. I. 200 parts of Pigment Red 177, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, this kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a violet pigment were obtained.

  The pigment refined as described above was used, and the rotational speed was 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution.

〔composition〕
Pigment Red 254 (average primary particle diameter 25 nm) 90 parts Pigment Red 177 (average primary particle diameter 25 nm) 10 parts Diketopyrrolopyrrole derivative 10 parts benzyl methacrylate / methacrylic acid (= 70/30 [mol] Ratio]) propylene glycol monomethyl ether acetate solution of copolymer (weight average molecular weight: 5,000) (solid content 40%) ... 75 parts, dispersant (BYK-161, manufactured by BYK) ... 35 parts, propylene glycol monomethyl Ether acetate: 495 parts

  Subsequently, the mixed solution obtained above was further subjected to co-dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads.

  Components of the following composition were further added to the obtained pigment dispersion and mixed by stirring to prepare a colored curable composition 3 (color resist solution) of the present invention. In addition, the pigment density | concentration in the total solid of the obtained colored curable composition 3 was 48%.

〔composition〕
Dipentaerythritol hexaacrylate 30 parts 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 10 parts (photopolymerization initiator)
・ 4,4′-bis (diethylamino) benzophenone (sensitizing dye) 5 parts ・ 2-mercaptobenzothiazole (hydrogen-donating compound) 5 parts ・ The above (d1) phenol group-containing copolymer (weight average molecular weight) 10,000) ... 5 parts propylene glycol monomethyl ether acetate ... 310 parts

Example 4
In Example 1, in place of the (d1) phenol group-containing copolymer, the following (d2) phenol group-containing copolymer (weight average molecular weight 10,000) was used. A colored curable composition 4 was obtained in the same manner.

(Example 5)
In Example 2, Example 2 was used except that the above (d2) phenol group-containing copolymer (weight average molecular weight 10,000) was used instead of the above (d1) phenol group-containing copolymer. A colored curable composition 5 was obtained in the same manner.

(Example 6)
In Example 3, in place of the (d1) phenol group-containing copolymer, the above (d2) phenol group-containing copolymer (weight average molecular weight 10,000) was used. A colored curable composition 6 was obtained in the same manner.

(Comparative Example 1)
In Example 1, the colored curable composition 7 was obtained by the same method as Example 1 except not having added said (d1) phenol group containing copolymer.

(Comparative Example 2)
In Example 2, the colored curable composition 8 was obtained by the same method as Example 2 except not having added said (d1) phenol group containing copolymer.

(Comparative Example 3)
In Example 3, a colored curable composition 9 was obtained in the same manner as in Example 3 except that the (d1) phenol group-containing copolymer was not added.

(Comparative Example 4)
In Example 1, in place of the (d1) phenol group-containing copolymer, the following (d3) polyhydroxystyrene (weight average molecular weight 10,000) was used, except that it was the same as Example 1. The colored curable composition 10 was obtained by the method.

(Comparative Example 5)
In Example 2, in place of the above (d1) phenol group-containing copolymer, the same as in Example 2 except that the above (d3) polyhydroxystyrene (weight average molecular weight 10,000) was used. The colored curable composition 11 was obtained by the method.

(Comparative Example 6)
In Example 3, in place of the (d1) phenol group-containing copolymer, the same as (d3) polyhydroxystyrene (weight average molecular weight 10,000) was used. The colored curable composition 12 was obtained by the method.

  Using the colored curable compositions 1 to 12 prepared as described above, color filters were produced and evaluated as follows. The results are shown in Table 1.

(2. Production of color filter)
2-1. Formation of Colored Curable Composition Layer Using a pigment-containing colored curable composition obtained as described above as a resist solution, slit coating is performed on a 550 mm × 650 mm glass substrate under the following conditions, and then waiting for 10 minutes. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a colored curable composition layer.
The slit application conditions are as follows.

(Slit application conditions)
Gap at the opening of the coating head tip: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and development Thereafter, the colored curable composition layer is exposed in a pattern with an ultrahigh pressure mercury lamp having an energy of 20.0 mW / cm ² for 2.5 seconds. After the exposure, the entire surface of the coating film is exposed to an organic developer (product). Name: CDK-1, covered with a 1.0% aqueous solution of Fuji Film Electronics Materials Co., Ltd., and rested for 60 seconds. After stationary, pure water was sprayed in a shower to wash away the developer, and a color filter having a colored pattern on the glass substrate was obtained.

2-3. Heat treatment In the color filter having the colored pattern obtained as described above, the hardness and cross-sectional shape of the colored pattern are observed and evaluated, and if necessary, the heat treatment (post) is performed in an oven at 230 ° C. for 0.5 hour. A color filter having a final coloring pattern was obtained.
Here, the hardness and cross-sectional shape of the colored pattern were observed and evaluated by the methods described later.

(3. Evaluation)
Using the colored curable composition prepared above, the exposure sensitivity of the colored curable composition layer formed on the glass substrate, the solubility and developability of the unexposed area in an alkaline developer, obtained after exposure and development The substrate adhesion, resolution, hardness, and cross-sectional shape of the colored pattern were evaluated as follows.

<Exposure sensitivity of colored curable composition layer>
The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The results of measurement evaluation are shown in Table 1 below.

<Solubility in alkaline developer>
In the exposure step, the behavior when the region not irradiated with light (unexposed portion) was dissolved in the developer was evaluated based on the following criteria. The evaluation results are shown in Table 1 below.
○: Developed in a soluble manner.
X: The film was developed like a film.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability. The evaluation criteria are as follows. The evaluation results are shown in Table 1 below.
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not defects were generated in the colored pattern. The evaluation items were evaluated based on the following criteria. The evaluation results are shown in Table 1 below.
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

<Resolution>
In the exposure step, exposure was performed under the above conditions using a mask having a width of 15 μm, development was performed, the line width of the colored pattern obtained was measured, and the resolution was evaluated. The evaluation criteria are as follows. The evaluation results are shown in Table 1 below.
○: A colored pattern having a high resolution of 14 μm or more and 16 μm or less was obtained.
Δ: A colored pattern having a standard resolution of 16 μm or more and 18 μm or less was obtained.
X: A colored pattern having a low resolution of 18 μm or more was obtained.

<Colored pattern hardness>
After the development step, the micro hardness of the formed colored pattern was evaluated by a nanoindenter (Nanoindenter SA2, manufactured by MTS SYSTEM) according to the following criteria. The evaluation results are shown in Table 1 below.
○: The pattern hardness (H) is 0.2 GPa or more, and has a sufficient pattern hardness.
Δ: Pattern hardness (H) is 0.1 GPa or more and less than 0.2 GPa, and has a standard pattern hardness after development.
X: Pattern hardness (H) is less than 0.1 GPa, and pattern hardness after development is insufficient.
When the hardness was evaluated as “×”, post-baking was performed as described above to obtain a color filter.

<Pattern cross-sectional shape>
After completion of the development process, the glass substrate having a colored pattern is cut using a diamond cutter, and the cross-sectional shape of the formed colored pattern is described below using a field emission scanning electron microscope (manufactured by S-4800 HITACHI). Evaluation was performed based on the criteria. The evaluation results are shown in Table 1 below.
A: Tapered angle in the range of 30 to less than 70 degrees (forward taper)
○: Tapered angle in the range of 70 to less than 90 degrees (forward taper)
Δ: Taper angle is 90 degrees (rectangular)
X: The taper angle exceeds 90 degrees (reverse taper)
When the hardness was evaluated as “×”, post-baking was performed as described above to obtain a color filter.

In Examples 1 to 6 using the phenol group-containing copolymer (d1) or (d2), the exposure sensitivity, developer solubility, developability, adhesion to the substrate, resolution, pattern hardness, and cross-sectional shape are all The color filter was able to be produced by skipping the post-baking step.
In Comparative Examples 1 to 3 in which the phenol group-containing copolymer was not added, the developer solubility was film-removal, the development residue was confirmed, and the resolution was also low. Moreover, although the pattern hardness was sufficient, since the shape after development was inversely tapered, it was necessary to produce a color filter through a post-baking process. Further, in Comparative Examples 4 to 6 in which (d3) polyhydroxystyrene was added instead of adding the phenol group-containing copolymer of (d1) and (d2), the developer solubility was soluble and the development residue was also confirmed. Although the resolution is high, the exposure sensitivity, the substrate adhesion, the pattern hardness are low, and the post-development shape is a reverse taper. Therefore, it is necessary to produce a color filter through a post-baking process.

Claims (10)

  (A) a colorant, (b) a polymerizable compound having an ethylenically unsaturated double bond, (c) a photopolymerization initiator, (d) a compound in which a polymerization-inhibited site and a surface orientation site are linked, and ( e) A colored curable composition containing a solvent. The compound (d) in which the polymerization inhibition site and the surface alignment site are linked includes a unit skeleton having a phenol group represented by the following general formula (1) and a unit skeleton having a fluoro group The colored curable composition according to claim 1, which is a coalescence.

[In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represents a hydrogen atom or a substituent. ] The unit skeleton having a phenol group represented by the general formula (1) is a unit skeleton represented by the following general formula (2), general formula (3), or general formula (4). The colored curable composition according to claim 2.

[In General Formula (2) to General Formula (4), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent, and R ⁵ represents a hydrogen atom or a methyl group. , R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X and Y each independently represent an alkylene group having 1 to 6 carbon atoms. ] The colored curable composition according to claim 2 or 3, wherein the unit skeleton having a fluoro group is a unit skeleton having a group represented by the following general formula (5).

[In general formula (5), n represents the arbitrary integers of 1-20. ] The colored curable composition according to any one of claims 2 to 4, wherein the unit skeleton having the fluoro group is a unit skeleton represented by the following general formula (6).

[In General Formula (6), R ⁷ represents a hydrogen atom or a methyl group, Z represents an alkylene group having 1 to 6 carbon atoms, and n represents an arbitrary integer of 1 to 20. ]   The content of the (a) colorant is 20% or more and 60% or less by mass fraction with respect to the total solid content of the colored curable composition. The colored curable composition according to Item.   A colored pattern formed from the colored curable composition according to any one of claims 1 to 6.   A color filter comprising the colored pattern according to claim 7 on a substrate.   A colored curable composition according to any one of claims 1 to 6 is used on a substrate, and an arbitrary colored pattern is formed by repeating coating, pre-baking, exposure, and development. A method for manufacturing a color filter.   A liquid crystal display device comprising the color filter according to claim 8.