JP5591509B2 - Colored curable composition, color filter and method for producing the same, and solid-state imaging device, image display device, liquid crystal display, and organic EL display using the same - Google Patents

Description

  The present invention relates to a color curable composition suitable for a color resist used for forming a colored pixel by a photolithographic method, an inkjet ink used for forming a colored pixel by an ink jet method, a color filter using the same, a method for producing the same, and The present invention relates to a solid-state imaging device using color filters, an image display device, a liquid crystal display, and an organic EL display.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays is also awaited due to the demand for higher image quality.
On the other hand, the demand for solid-state imaging devices such as CCD image sensors has greatly increased due to the spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and colors light passing therethrough in an image display device or a solid-state imaging device. And plays the role of breaking down into the three primary colors.

  The colorant used in the color filter is required to have the following properties in common. In other words, it has favorable light absorption characteristics in terms of color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for it to be excellent in toughness under the environmental conditions in use, for example, heat resistance, light resistance, wet heat resistance, etc., to have a large molar extinction coefficient and to be capable of being thinned.

  A pigment dispersion method is used as one of methods for producing a color filter used for a solid-state imaging device, a liquid crystal display, an organic EL display, and the like. A method for producing a color filter by a photolithography method or an inkjet method by a pigment dispersion method is stable to light and heat because a pigment is used.

  In order to produce a color filter by a photolithographic method, a radiation-sensitive composition is applied on a substrate with a spin coater, slit coater, roll coater, etc., dried to form a coating film, and the coating film is subjected to pattern exposure and development. By doing so, a colored pixel is obtained. A color filter can be produced by repeating this operation for the number of hues. Since the patterning is performed by light, sufficient positional accuracy can be secured, and the method is widely used as a method suitable for producing a high-definition color filter having a large screen used for a liquid crystal display, an organic EL display or the like.

  In a color filter for a solid-state imaging device, exposure is performed through a fine pattern mask, followed by development with an alkaline solution, and an unexposed portion is dissolved in an alkaline developer to form a fine pattern. It is difficult to adjust the solubility (developability) of the exposed area.

  In recent years, there has been a demand for higher definition of color filters for solid-state imaging devices. Therefore, in order to suppress the occurrence of color unevenness due to the coarse particles of the pigment, it is desired to make the pigment finer. In addition, in liquid crystal displays and organic EL displays, color filters manufactured by the photolithography method using the pigment dispersion method have the advantage of excellent light resistance and heat resistance, as well as light scattering caused by coarse pigment particles. Therefore, since there is a problem such as a decrease in contrast and an increase in haze, it is desired to make the pigment finer. However, since the finely divided pigment is easily aggregated, it is necessary to provide dispersibility.

  On the other hand, it has been studied to use a dye as a colorant instead of the pigment dispersion method (see, for example, Patent Document 1). When a dye is used as a colorant, high resolution is achieved by solving the problem of color unevenness and roughness in the color filter for solid-state image sensors, and optical properties such as contrast and haze are improved in liquid crystal displays and organic EL displays. Each is expected. Ink jet methods using dyes generally have high ejection stability, and it is expected that the ink ejection state can be easily recovered by wiping or purging even when nozzle clogging occurs due to an increase in ink viscosity.

  However, since ordinary dyes have low developability in an alkaline solution, the colored curable composition containing the dye has a problem that the unexposed area has poor solubility (developability) and cannot form a pattern. And in order to provide developability to dye, the method of copolymerizing the monomer which has a pigment group, and the monomer which has an alkali-soluble group is disclosed (refer patent document 2, 3, 4).

Japanese Patent Laying-Open No. 2005-316012 JP 2007-139906 A JP 2007-138051 A Japanese Patent No. 3736221

  By using a copolymer of a monomer having a dye group and a monomer having an alkali-soluble group, developability can be obtained as described above. However, it has been found that when the copolymer and the pigment dispersion are used in combination in order to obtain color density, light resistance, and heat resistance, coating unevenness and color unevenness may occur. Further, when the pattern is formed in this state, there arises a problem that the pattern shape is deteriorated and a problem of color unevenness.

An object of the present invention is to provide a colored curable composition capable of forming a colored cured film with suppressed color unevenness.
Moreover, this invention makes it a subject to provide the colored curable composition excellent in applicability | paintability and pattern moldability, when it uses for the photolitho method.
Furthermore, this invention makes it a subject to provide image display devices, such as a color filter provided with the coloring pattern in which the color nonuniformity was suppressed, the solid-state image sensor provided with the said color filter, a liquid crystal display, and an organic electroluminescent display.
Another object of the present invention is to provide a color filter having a good pattern shape, a method for producing the color filter, and an image display device such as a solid-state imaging device, a liquid crystal display, or an organic EL display provided with the color filter.

As a result of detailed studies, the present inventors have found that the occurrence of color unevenness is suppressed by using a dye group-containing resin and a pigment dispersion containing a specific repeating unit. Furthermore, the knowledge which the applicability | paintability and pattern formation property improved by using the colored curable composition containing the resin and pigment dispersion liquid for manufacture of the color filter by a photolithographic method was acquired. The present invention has been achieved based on such findings.
Specific means for solving the above-mentioned problems are as follows.

<1> (A) Resin having a repeating unit represented by general formula (a) and a repeating unit represented by general formula (b), (B) a pigment dispersion, (C) a photopolymerization initiator, (D) A polymerizable curable composition containing a polymerizable compound.

In general formula (a), X ¹ represents a polymer main chain. Y ¹ represents a single bond or a divalent linking group. Q represents a phthalocyanine dye residue or a dipyrromethene dye residue.

In the general formula (b), ^{X 2} represents a polymer main chain represented by any one of the following formulas ^{(X 1 -1) ~ (X} 1 -12). Y ² represents a divalent linking group represented by the following general formula (b ′) . Z represents an alkali-soluble group.
In the following general formula (b ′), A represents an alkylene group, a cycloalkylene group, or an arylene group. B is _{-CO 2 -, - O 2 C} -, - O -, - NH -, - representing the S-. C represents an alkylene group, a cycloalkylene group, or an arylene group. n represents an integer of 0 to 10.

<2> X ¹ in the general formula (a) and X ² in the general formula (b) are each independently a polymer main group represented by the following formula (X ¹ -1) or (X ¹ -2). The colored curable composition according to <1>, which represents a chain.
<3> Z in the general formula (b) is a colored curable composition according to <1> or <2>, which represents —CO ₂ H.
<4> The ratio of the repeating unit represented by the general formula (b) to the whole (A) resin is 5% by mass or more and 60% by mass or less, according to any one of <1> to <3>. It is the colored curable composition of description.
< 5 > The coloring according to any one of <1> to <4>, wherein the pigment contained in the (B) pigment dispersion is a pigment selected from a blue pigment, a violet color pigment, and a mixture thereof. It is a curable composition.

< 6 > It is a color filter provided with the coloring pattern which uses the colored curable composition of any one of <1> - < 5 >.

< 7 > A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of <1> to < 5 > on a support, and a pattern shape with respect to the colored layer And a developing step of developing the colored layer after the exposure to form a colored pattern.

< 8 > The method for producing a color filter according to < 7 >, including an ultraviolet irradiation step of irradiating the colored pattern formed by the developing step with ultraviolet rays.

< 9 > A solid-state imaging device including the color filter according to < 6 >.
< 10 > An image display device comprising the color filter according to < 6 >.
< 11 > A liquid crystal display comprising the color filter according to < 6 >.
< 12 > An organic EL display including the color filter according to < 6 >.

According to the present invention, a colored curable composition for forming a colored cured film with suppressed color unevenness is provided.
Moreover, according to this invention, when used for the photolithographic method, the colored curable composition excellent in applicability | paintability and pattern moldability is provided.
Furthermore, according to the present invention, there are provided a color filter having a colored pattern in which color unevenness is suppressed, and an image display device such as a solid-state imaging device, a liquid crystal display, and an organic EL display having the color filter.
In addition, according to the present invention, there are provided a color filter having a good pattern shape, a method for manufacturing the color filter, and an image display device such as a solid-state imaging device, a liquid crystal display, and an organic EL display provided with the color filter.

  Below, the coloring curable composition of this invention, a color filter, and the manufacturing method of a color filter are explained in full detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

-Colored curable composition-
The colored curable composition of the present invention comprises (A) a resin having a repeating unit represented by the general formula (a) and a repeating unit represented by the general formula (b) (hereinafter also referred to as (A) a specific resin). And (B) a pigment dispersion.
The colored curable composition of the present invention is characterized by being cured by light, and further comprises (C) a photopolymerization initiator and (D) a polymerizable compound, and, if necessary, a solvent and a binder. , And other components such as a cross-linking agent. The colored curable composition is cured at least by light, but may have a property of being cured by heat.

In the colored curable composition of the present invention, color unevenness of the colored cured film formed by the above configuration is suppressed. The reason is not clear, but is presumed as follows. That is, (A) the substituent represented by Q in the general formula (a) of the specific resin has high affinity for the pigment contained in the (B) pigment dispersion, and (A) the specific resin has the general formula By having the repeating unit represented by (a) and the repeating unit represented by the general formula (b), (B) a pigment dispersion, (D) a polymerizable compound, and (E) used as necessary. Since affinity with a solvent improves, it is estimated that aggregation of a pigment is suppressed and color nonuniformity is suppressed.
Moreover, when the colored curable composition of this invention is the said structure, when it is used for manufacture of the color filter by a photolitho method, applicability | paintability and pattern formation property are favorable. The reason is that, as described above, (A) the specific resin interacts with (B) the pigment contained in the pigment dispersion, (D) the polymerizable compound, and (E) the solvent used as necessary. Phase separation that deteriorates coating properties and pattern formability hardly occurs, and a uniform coating film is formed. (A) Due to the structure of the specific resin, it has better affinity for an alkaline developer. Therefore, it is presumed that the pattern forming property is also excellent.

<(A) Specific resin of the present invention>
The specific resin (A) used in the present invention will be described in detail.
The (A) specific resin used in the present invention has a repeating unit represented by the general formula (a) and a repeating unit represented by the general formula (b). Hereinafter, the general formula (a) and the general formula (b) will be sequentially described.
In the present invention, X ^{2 in the} general formula (b) represents a polymer main chain represented by any of the following formulas (X ¹ -1) to (X ¹ -12), and Y ² represents the following general formula (b The form which represents the bivalent coupling group shown by ') is applied.
<Repeating unit represented by general formula (a)>

In general formula (a), X ¹ represents a polymer main chain. As the polymer main chain, a known polymer main chain can be selected, and examples include general formulas (X ¹ -1) to (X ¹ -12). preferably formula ^{(X 1 -1) ~ (X} 1 -3) and ^{(X 1 -10) ~ (X} 1 -12), the general formula ^(X 1 -1) and ^(X 1 -2) is most preferred.

In general formula (a), Y ¹ represents a single bond or a divalent linking group. As the linking group, an alkylene group and an arylene group are preferable, and an alkylene group having 1 to 10 carbon atoms is particularly preferable.
The linking group may contain a hetero atom such as an oxygen atom or a sulfur atom in the carbon chain, and may have a substituent such as a carboxyl group. As said hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom is the most preferable.
Among the above, the linking group represented by Y ¹ in the general formula (a) is particularly preferably an unsubstituted linear alkylene group containing no hetero atom.
In the general formula (a), specific examples of the linking group represented by Y ¹ include the following linking groups.

In formula (a), the linking group represented by ^{Y 1,} among other linking groups shown as the examples _{above, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 - _{, -CH 2 CH (OH) CH} 2 -, - CH 2 CH 2 CMe 2 - is most preferred.

In general formula (a), Q represents a residue obtained by removing one hydrogen atom from a phthalocyanine dye or a dipyrromethene dye.
First, the phthalocyanine dye residue will be described. Examples of the phthalocyanine dye residue include phthalocyanine dye residues represented by the general formula (A).

In general formula (A), M ¹ represents metals, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently form a 6-membered ring composed of atoms selected from carbon atoms and nitrogen atoms. Represents the atomic group necessary to However, one hydrogen atom is removed from one selected from Z ¹ , Z ² , Z ³ , and Z ⁴ and linked to Y ¹ in the general formula (a).

The general formula (A) will be described in detail.
In the general formula (A), examples of the metal represented by M ¹ include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. Includes metal atoms, metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂

In the general formula (A), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom necessary for forming a 6-membered ring composed of an atom selected from a carbon atom and a nitrogen atom. Represents a group. The 6-membered ring may be a saturated ring or an unsaturated ring, and may be unsubstituted or have a substituent. Specific examples of the substituent include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms). Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, octyl and the like, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, and 1 carbon atom) And more preferably an alkoxy group having 5 to 5. Specifically, methoxy, ethoxy, propoxy, butoxy, tert-butoxy and the like, an aryl group (preferably an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms). More specifically, phenyl, naphthyl, etc.), sulfo group, carboxyl group, hydroxyl group, etc. It is below. When the 6-membered ring has two or more substituents, these substituents may be the same or different. Further, the 6-membered ring may be condensed with another 5-membered or 6-membered ring.
The 6-membered ring includes a benzene ring, a cyclohexane ring and the like.
Among the phthalocyanine dye residues represented by the general formula (A), a residue derived from a phthalocyanine dye represented by the following general formula (A-1) is particularly preferable.

In formula (A-1), ^{M 2} has the same meaning as ^{M 1} in formula (A), is the same a preferred embodiment thereof.
In the general formula (A-1), R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is a further substitutable group. May be substituted with the groups described above for the substituents, and when substituted with two or more substituents, these substituents may be the same or different. However, one hydrogen atom is removed from one selected from R ^{101 to} R ¹¹⁶ and linked to Y ¹ represented by the general formula (a).
Among the above, the substituents represented by R ^{101 to} R ¹¹⁶ are halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups having 1 to 5 carbon atoms, sulfo groups, carboxyl groups, and hydroxyl groups. Is preferred.

  Next, the dipyrromethene dye residue will be described. The dipyrromethene dye residue is represented by the general formula (B).

In general formula (B), R < ² > -R < ⁵ > represents a hydrogen atom or a substituent each independently. Specific examples of the substituent are the same as the substituents in Z ¹ , Z ² , Z ³ and Z ⁴ , and among them, R ² and R ⁵ are preferably an alkoxycarbonyl group, an amide group or a cyano group, R ³ and R ⁴ are preferably an alkyl group, a cycloalkyl group, or an aryl group. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and among them, a hydrogen atom is preferable.
Ma represents a metal or a metal compound. Specific examples of the metal or metal compound is the same as the M ^1.
X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom. Represent. X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom. As X ³ and X ⁴ , an oxygen atom is most preferable among the above.

Y ³ and Y ⁴ each independently represent NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, Or represents a carbon atom. Among Y ³ and Y ⁴ , NH is preferable.
R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ³ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ⁴ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. R ⁸ and R ⁹ are preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and most preferably a branched alkyl group having 1 to 10 carbon atoms or a phenyl group. R ⁸ and R ⁹ may be substituted with an alkoxy group, an alkylthio group, an arylthio group, or the like.

X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. Specific examples of the group represented by X ^5, for example, an acetoxy group, 2-hydroxy-propanoyl group, a pivaloyloxy group, mesyl group, and the like tosyl group.
However, one hydrogen atom is removed from one selected from R ^{2 to} R ⁵ , R ^{7 to} R ⁹ , and X ⁵ to connect with Y ¹ in the general formula (a).

  Although the specific example of general formula (A) and general formula (B) is given, this invention is not limited to this.

  Specific examples of the repeating unit represented by the general formula (a) are given below, but the present invention is not limited thereto.

<Repeating unit represented by general formula (b)>

In the general formula (b), ^{X 2} represents a polymer backbone. Specific examples and preferred ranges of X ² are the same as X ¹ in the general formula (a). Y ² represents a divalent linking group. Y ² is preferably an alkylene group or an arylene group, and the carbon chain may contain a hetero atom such as an oxygen atom or a sulfur atom, and may have a substituent such as a carboxyl group. Specifically, Y ² is preferably a linking group shown below.

In general formula (b ′), A represents an alkylene group, a cycloalkylene group, or an arylene group, and an alkylene group having 1 to 10 carbon atoms is particularly preferable, and an alkylene group having 1 to 5 carbon atoms is preferable. B is _{-CO 2 -, - O 2 C} -, - O -, - NH -, - represents a S-, particularly _{-CO 2 -, - O 2 C} -, - O- are preferred. C represents an alkylene group, a cycloalkylene group, or an arylene group, and an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, and a phenylene group are particularly preferable. n represents an integer of 0 to 10, and n is preferably 0 to 5.

  In general formula (b), Z represents an alkali-soluble group, but carboxylic acid, phosphoric acid and sulfonic acid are preferred, and carboxylic acid is most preferred.

Preferable examples of the repeating unit represented by the general formula (b) are listed below, but the present invention is not limited thereto.

  (A) The specific resin may contain (c) other repeating units in order to adjust curability and developability. (C) Other repeating units include (meth) acrylic acid alkyl, (meth) acrylic acid aralkyl, styrene, alkylene oxide-containing monomers (for example, BLEMMER PE200, etc.), polymerizable group-containing repeating units (for example, carboxylic acid) Glycidyl methacrylate adduct), N, N-dimethylacrylamide, N-isopropylacrylamide and the like. (C) Preferred examples of other repeating units are shown below, but the present invention is not limited thereto.

  The repeating unit represented by the general formula (a) is preferably contained in an amount of 50 to 95% by mass, more preferably 60 to 90% by mass, and more preferably 70 to 90% with respect to the (A) specific resin. More preferably, it is contained by mass%. Moreover, it is preferable that the repeating unit represented by general formula (b) is contained 5 to 60 mass% with respect to (A) specific resin, and it is preferable that 10 to 50 mass% is contained. Moreover, as (c) other repeating units, it is preferable to contain in 0-40 mass%.

The specific resin (A) of the present invention preferably has a weight average molecular weight measured by GPC of 4,000 to 50,000, and most preferably 5,000 to 30,000.
Although the specific example of (A) specific resin of this invention is shown here, this invention is not limited to this. The ratio (a) / (b) / (c) is a mass ratio.

<(B) Pigment dispersion>
The colored curable composition of the present invention contains (B) a pigment dispersion. The (B) pigment dispersion of the present invention contains (B-1) a pigment and (B-2) a pigment dispersant. Details will be described below.

<(B-1) Pigment>
As the pigment that the colored curable composition of the present invention has, conventionally known various inorganic pigments or organic pigments can be used.
Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling property, the average primary particle diameter of the pigment is 0.00. 005 μm to 0.1 μm is preferable, and 0.005 μm to 0.05 μm is more preferable.

  Examples of the inorganic pigment used in the colored curable composition of the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, Mention may be made of metal oxides such as titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

As an organic pigment that can be used in the colored curable composition of the present invention, for example,
C. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,17 3,174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195,196,197,198,199,200, 202, 203, 204, 205, 206, 207, 208;

C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266 267, 268, 269, 270, 271, 272, 273, 274, 275, 276;

C. I. Pigment Violet 1,1,1,2,2: 2,3,3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50;
C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 79 Changed to OH;
C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55;
C. I. Pigment brown 23, 25, 26;
C. I. Pigment black 1,7;
Examples thereof include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the colored curable composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.

  Examples of pigments that can be preferably used in the present invention include blue pigments and violet color pigments, and the following are particularly preferable. However, the present invention is not limited to these.

C. I. Pigment violet 19, 23, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66

  Of these pigments, C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Violet 23 is preferable from the viewpoint of color characteristics. These may be used as a mixture. The mass ratio of the blue pigment to the violet color pigment is preferably 100: 0 to 100: 100, and more preferably 100: 10 or less.

<(B-2) Dispersant>
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  The dispersant is preferably used in an amount of 10 to 70 parts by weight, and most preferably 30 to 60 parts by weight with respect to 100 parts by weight of the pigment.

<Pigment derivative>
The pigment dispersion of the present invention preferably further contains a pigment derivative.
The pigment derivative preferably has a structure in which a part of an organic pigment, anthraquinones or acridones is substituted with an acidic group, a basic group or a phthalimidomethyl group. Examples of the organic pigment constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, Anthraquinone pigments such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, Examples thereof include isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  As an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and those quaternary ammonium salts are preferable. Moreover, as a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is the most preferable.

  Although there is no restriction | limiting in particular in the usage-amount of a pigment derivative, It is preferable to use 5-50 mass parts with respect to 100 mass parts of pigments, and it is more preferable to use 10-30 mass parts.

<Other ingredients>
In addition to the above components, the pigment dispersion may contain a polymer compound such as an alkali-soluble resin, if necessary. Polar groups such as acid groups contained in the alkali-soluble resin are considered to be effective for the dispersion of the pigment, and are often effective for the dispersion stability of the pigment dispersion.

The pigment dispersion may be used in combination with other dyes. There is no restriction | limiting in particular as another pigment | dye, The well-known pigment | dye conventionally used as a color filter use can be used. For example, JP 2002-14220, JP 2002-14221, JP 2002-14222, JP 2002-14223, US Pat. No. 5,667,920, US Pat. , 059,500 specification, and the like.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used. These pigments may be dyes or pigments.

The pigment dispersion may contain a solvent as a dispersion medium.
The solvent is selected depending on the solubility of each component contained in the pigment dispersion and the coating properties when the pigment dispersion is applied to the curable composition. As the solvent, esters, ethers, ketones, and aromatic hydrocarbons are used. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate (PGMEA) are preferred.
As content of the solvent in a pigment dispersion liquid, 50-95 mass% is preferable, and 70-90 mass% is more preferable.

<(C) Photopolymerization initiator>
The colored curable composition of the present invention contains (C) a photopolymerization initiator in order to improve sensitivity and pattern formation.
The photopolymerization initiator in the present invention is a compound that decomposes by light and initiates and accelerates polymerization of a polymerizable component such as (D) a polymerizable compound described later, and particularly absorbs in a wavelength region of 300 nm to 500 nm. It is preferable that it is a compound which has. The (C) photopolymerization initiator may have a property of starting polymerization by heat in addition to the property of starting polymerization by light as described above.
Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator used in the present invention include organic halogenated compounds, oxocidiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples include metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfonic acid compounds, oxime compounds, onium salt compounds, acylphosphine (oxide) compounds, and alkylamino compounds.
Hereinafter, each of these compounds will be described in detail.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP Sho 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxodiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.
Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl-o-benzoylbenzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfonic acid compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.

  Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it is preferable that two or more are substituted with an electron donating group such as an alkyl group, an alkoxy group, and an aryloxy group. In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and US Pat. No. 4,933. , 377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, German Patent No. Examples include sulfonium salts described in the specifications of 2,904,626, 3,604,580, and 3,604,581, and are preferably substituted with an electron-withdrawing group from the viewpoint of stability and sensitivity. It is preferable that The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

  As the (C) photopolymerization initiator used in the present invention, the above-described initiators can be arbitrarily used, but from the viewpoint of exposure sensitivity, more preferably a triazine compound (s-triazine) of an organic halogenated compound. Compound), ketal compound, benzoin compound, metallocene compound, hexaarylbiimidazole compound, oxime compound, acylphosphine (oxide) compound, hexaalkylamino compound, triazine compound, oxime compound, hexaarylbiimidazole compound At least one compound selected from the group consisting of a compound and an alkylamino compound is more preferable, and an oxime compound is most preferable.

  In particular, when the colored curable composition of the present invention is used for forming colored pixels in a color filter of a solid-state imaging device, the amount of the photopolymerization initiator added is reduced because the pigment concentration in the composition is high due to the formulation. , The sensitivity may decrease. When exposure is performed with a stepper, use of an initiator that generates a halogen-containing compound during exposure, such as a triazine compound, may cause corrosion of the equipment. Considering these, as the photopolymerization initiator that satisfies the sensitivity and various performances, an oxime compound is preferable, and an oxime compound having absorption at 365 nm is most preferable.

  In the present invention, among the oxime compounds, a compound represented by the following general formula (d) is preferable from the viewpoints of sensitivity, stability at the time of diameter, and coloring during post-heating. Moreover, Irgacure OXE-01, OXE-02, etc. manufactured by Ciba Specialty Chemicals are also preferable.

In the general formula (d), R ²² and X ²² each independently represent a monovalent substituent, A ²² represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

R ²² is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

A ²² is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. , An alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X ²² may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthioxy group, substituted An arylthio group which may have a group and an amino group which may have a substituent are preferable.
Moreover, n in general formula (d) is preferably an integer of 1 to 2.

  Specific examples of oxime compounds suitable for the colored curable composition of the present invention are shown below, but the present invention is not limited thereto.

  (C) It is preferable that content of a photoinitiator is 0.1 mass%-50 mass% with respect to the total solid of the colored curable composition of this invention, More preferably, it is 0.5 mass%. -30% by mass, particularly preferably 1% by mass to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(D) Polymerizable compound>
The curable composition of the present invention contains (D) a polymerizable compound.
The polymerizable compound (D) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. It is chosen from the compound which has.
Such compounds are widely known in the industrial field, and can be used without any particular limitation in the present invention.

  These have chemical forms such as monomers, prepolymers (ie, dimers, trimers, and oligomers), or mixtures or copolymers thereof. Examples of monomers and copolymers thereof include, for example, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters or amides thereof. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group and a monofunctional or polyfunctional isocyanate or epoxy, and a hydroxy group, A dehydration condensation reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as an amino group or a mercapto group and a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for the unsaturated carboxylic acid.

Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid ester, methacrylic acid ester, itaconic acid ester, and the like.
Examples of acrylic esters include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate. , Trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol diacryl Over DOO, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers, and isocyanuric acid EO-modified triacrylate.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, for example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. In particular, pentaerythritol triacrylate succinic acid monoester is preferable from the viewpoint of developability and sensitivity.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in a compound represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. Etc.

Formula ^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these (D) polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a colored curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, the compound containing a carboxylic acid group or EO modified body structure is preferable from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  In addition, the selection and use method of the polymerizable compound is an important factor for the compatibility and dispersibility with other components (eg, resin, photopolymerization initiator, pigment) in the colored curable composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate modified EO, dipentaerythritol hexaacrylate EO modified, pentaerythritol triacrylate succinic acid monoester and the like are preferred, and commercially available products include urethane oligomer UAS-10. , UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is preferable.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Pentaerythritol hexaacrylate EO modified product, pentaerythritol triacrylate succinic acid monoester, etc. are commercially available products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 T-600 and AI-600 (manufactured by Kyoeisha) are more preferred.

  The content of the polymerizable compound (D) in the present invention is preferably 1% by mass to 90% by mass and preferably 5% by mass to 80% by mass in the solid content of the colored curable composition of the present invention. More preferably, the content is more preferably 10% by mass to 70% by mass.

<(E) Solvent>
Although the use of the colored curable composition of the present invention is not particularly limited, specifically, for example, as described later, it is used for production of a color filter by a photolithographic method, production of a color filter by an ink jet method, or the like. And the (E) solvent and other additive which are mentioned later are used suitably as needed in consideration of a use etc.
First, the case where the colored curable composition of this invention is used for manufacture of the color filter by a photolitho method is demonstrated. The colored curable composition of the present invention used for the photolithography method preferably has (E) a solvent.
(E) As a solvent, the liquid selected from the organic solvent shown below is mentioned, for example, The solubility of each component contained in a pigment dispersion liquid, and the applicability | paintability at the time of applying to a colored curable composition These are selected in consideration of the above and are not particularly limited as long as these desired physical properties are satisfied, but are preferably selected in consideration of safety.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Glycol propyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; and aromatic hydrocarbons, e.g., toluene, xylene and the like; are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  As content of the (E) solvent in the colored curable composition of this invention, 50-90 mass% is preferable, 60-95 mass% is more preferable, 70-90 mass% is the most preferable. When the content of the solvent is within the above range, it is advantageous in terms of suppressing the generation of foreign matter. In addition, when using a colored curable composition for manufacture of the color filter by an inkjet method, the one where content of (E) solvent is small is preferable from a sclerosing | hardenable viewpoint so that it may mention later, (E) Solvent is not used. There can also be a form.

<Various additives>
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended. Examples of these include additives described in [0274] to [0276] of JP-A-2008-292970.

<Preparation method of colored curable composition>
In preparing the colored curable composition of the present invention, the above-described components of the composition may be blended together, or may be blended sequentially after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. A composition may be prepared by dissolving all the components in a solvent at the same time. If necessary, each component is appropriately made into two or more solutions, and these solutions are mixed at the time of use (at the time of application). And may be prepared as a composition.
The composition prepared as described above is preferably filtered after using a filter having a pore size of 0.01 to 3.0 μm, more preferably a pore size of about 0.05 to 0.5 μm, and then used. You can also.

  The colored curable composition of the present invention can be suitably used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (for example, CCDs, CMOSs, etc.). In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.

When the colored curable composition of the present invention is used, for example, in the production of a color filter by a photolithographic method, the colored pattern is formed in a thin film with a very small size, and a solid rectangular imaging profile requiring a good rectangular cross-sectional profile is required. It is particularly suitable for forming a color filter.
Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the amount of colorant increases. As a result, the line width sensitivity is deteriorated and the DOF margin is narrowed. As a result, the pattern formability is easily impaired. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased and the pattern is easily peeled off in the low exposure area. In this case, heat sagging is likely to occur when heat treatment such as post-baking is performed. These are particularly remarkable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).
On the other hand, when the colored curable composition of the present invention is used, a color filter having a good cross-sectional profile can be produced with excellent pattern formation even with the pixel pattern size of 2 μm or less as described above.

<Pattern formation method using colored curable composition>
A method for forming a color filter by a photolithography method using the colored curable composition described in the present specification includes a colored layer forming step of forming a colored layer by applying a colored curable composition on a support, An exposure step of exposing the colored layer in a pattern; and a development step of developing the colored layer after the exposure to form a pattern. Specifically, for example, JP-A-2008-292970 And the methods described in [0277] to [0284] of Japanese Patent Publication.

-Post-curing process-
In this invention, it is preferable to implement the post-curing process which further hardens the obtained pattern further after the process of forming a pattern by above-described image development.
The post-curing step is performed by heating (post-heating) and / or exposure (post-exposure such as ultraviolet irradiation), and the step of further curing the obtained pattern to form a colored layer for forming the next color pattern, etc. Thus, it is possible to prevent dissolution of the pattern and improve the solvent resistance of the pixel of the obtained color filter.
The post-curing step is preferably an ultraviolet irradiation step by ultraviolet irradiation.

-Post-curing process UV irradiation (UV irradiation process)-
In the ultraviolet irradiation process, the pattern is cured by post-exposure. More specifically, the pattern after performing a developing process in the pattern formation step, ultraviolet light exposure amount in the exposure process before development [mJ / cm ^2] of 10 times or more of the irradiation light amount [mJ / cm ^2] Irradiate (UV light). By irradiating the developed pattern with UV light for a predetermined time between the development processing in the pattern forming step and the heat treatment described later, it is possible to effectively prevent color migration when heated later. If the irradiation light quantity in this step is less than 10 times, color transfer between colored pixels or between upper and lower layers may not be prevented.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

  The post-exposure can be performed with g-line, h-line, i-line, KrF, ArF, UV light, electron beam, X-ray, etc., but g-line, h-line, i-line, UV light is preferable, and UV is particularly preferable. Light is preferred. When performing irradiation with UV light (UV cure), it is preferable to carry out at a low temperature of 20 ° C. or more and 50 ° C. or less (preferably 25 ° C. or more and 40 ° C. or less). The wavelength of the UV light preferably includes a wavelength in the range of 200 to 300 nm. As the light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, or the like can be used. The irradiation time is 10 to 180 seconds, preferably 20 to 120 seconds, and more preferably 30 to 60 seconds.

As a light source for irradiating UV light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp, or the like can be used. Among them, the irradiated ultraviolet light includes light having a wavelength of 275 nm or less, and the irradiation illuminance [mW / cm ² ] of the light having a wavelength of 275 nm or less is 5% or more with respect to the integrated irradiation illuminance of all the wavelength light in the ultraviolet light. The thing which can irradiate the light which is is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

The integrated irradiation illuminance is a curve with the illuminance for each spectral wavelength (radiant energy passing through a unit area per unit time; [mW / m ² ]) as the vertical axis and the wavelength [nm] of light as the horizontal axis. When drawn, it means the sum (area) of the illuminance of each wavelength light included in the irradiation light.

The integrated irradiation illuminance in the ultraviolet light irradiated in the post-exposure in the ultraviolet irradiation step is preferably 200 mW / cm ² or more. When the integrated irradiation illuminance is 200 mW / cm ² or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. Among them, preferred is ^{250~2000mW / cm 2, 300~1000mW / cm} 2 is more preferable.
Moreover, it is preferable to implement post-heating at 100 to 300 degreeC using a hotplate or oven, More preferably, it is 150 to 250 degreeC. The post-heating time is preferably 30 seconds to 30000 seconds, and more preferably 60 seconds to 1000 seconds.

  In the post-curing step, post-exposure and post-heating may be used together. In this case, either may be performed first, but it is preferable to perform post-exposure prior to post-heating. This is because curing is promoted by post-exposure, thereby suppressing deformation of the shape due to heat sagging and soaking of the pattern seen in the post-heating process.

  The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of hues, a color filter configured in a desired number of hues by repeating the pattern formation step (and post-curing step if necessary) according to the desired number of colors. Can be produced.

<Coloring curable composition used for inkjet method>
Next, the case where the colored curable composition of this invention is used for manufacture of the color filter by an inkjet method is demonstrated. Since (A) the specific resin, (B) the pigment dispersion, (C) the photopolymerization initiator, and (D) the polymerizable compound are the same as the colored curable composition of the present invention used in the photolithography method, Description is omitted.

  The colored curable composition of the present invention used in the ink jet method may or may not contain (E) a solvent. Examples of the form in which the colored curable composition does not include the solvent (E) include a form in which the polymerizable compound (D) serves as a solvent.

  (E) Solvent is not particularly limited as long as the solubility of each component and the boiling point of (E) solvent described below are satisfied, but in particular, considering the solubility, applicability, and safety of the binder described below. It is preferable to be selected. (E) Specific examples of the solvent include the solvents described in paragraphs [0030] to [0040] of JP-A-2009-13206.

  (E) 30-90 mass% is preferable with respect to the coloring curable composition whole quantity, and, as for content of a solvent, 50-90 mass% is more preferable. When the amount is 30% by mass or more, the amount of ink ejected in one pixel is maintained, and the wetting and spreading of the ink in the pixel is good. Further, when the content is 90% by mass or less, the amount of components other than the solvent for forming a functional film (for example, a pixel) in the ink can be maintained at a predetermined amount or more. As a result, when forming a color filter, the required amount of ink per pixel does not increase too much. For example, when ink is applied to the concave portion partitioned by the partition wall by the ink jet method, the ink overflows from the concave portion. And the occurrence of color mixing with adjacent pixels can be suppressed.

  The colored curable composition of the present invention used in the ink jet method preferably contains a solvent having a high boiling point among the above-mentioned solvents from the viewpoints of ink dischargeability to the nozzle and wettability to the substrate. Since the solvent having a low boiling point evaporates quickly even on the ink jet head, it easily causes an increase in the viscosity of the ink on the head, precipitation of solids, and the like, and is often accompanied by a deterioration in dischargeability. Also, when the ink lands on the substrate surface and spreads on the substrate surface, the viscosity of the ink increases due to the evaporation of the solvent at the edge of the wet spread, and the phenomenon of pinning (PINING) causes the wetting and spreading. It may be suppressed.

  The boiling point of the solvent used in the colored curable composition of the present invention used in the ink jet method is preferably 130 to 280 ° C. If it is lower than 130 ° C., it may not be preferable in terms of the uniformity of the shape of pixels in the surface. If it is higher than 280 ° C., it may not be preferable in terms of solvent removal by pre-baking. The boiling point of the solvent means a boiling point under a pressure of 1 atm, and can be known from a property value table such as a compound dictionary (Chapman & Hall). These may be used alone or in combination of two or more.

  The colored curable composition of the present invention used in the ink jet method may contain the binder as necessary for the purpose of adjusting the viscosity and adjusting the ink hardness. As the binder, a binder resin that is simply dried and solidified such that it is composed only of a resin that is not polymerized by itself may be used. However, in order to impart sufficient strength, durability, and adhesion to the coating film, a binder that can cure the pixel by a polymerization reaction after forming a pixel pattern on the substrate by an inkjet method is used. For example, a binder that can be polymerized and cured, such as a photocurable binder that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder that can be polymerized and cured by heating. Can be used.

  Moreover, the colored curable composition of the present invention used in the ink jet method may contain a crosslinking agent. As the cross-linking agent, the curing agent and the accelerator described in Chapter 3 of “Review Epoxy Basic Fundamentals I” issued on November 19, 2003, published by the Epoxy Resin Technology Association, can be suitably used. Carboxylic anhydride or polyvalent carboxylic acid can be used.

  Moreover, you may use surfactant further for the coloring curable composition of this invention used for the inkjet method. As examples of the surfactant, those disclosed in JP-A-7-216276, paragraph [0021], JP-A-2003-337424, and JP-A-11-133600 are preferable. As mentioned. As for content of surfactant, 5 mass% or less is preferable with respect to coloring composition whole quantity.

  In addition, as other additives included as necessary in the colored curable composition of the present invention used in the inkjet method, other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706 An additive is mentioned.

For the production of the colored curable composition of the present invention used in the inkjet method, a known inkjet ink production method can be applied.
(D) When preparing a solution of the polymerizable compound, if the solubility of the material used in the solvent is low, heating, ultrasonic treatment, etc. within the range in which the polymerizable compound does not cause a polymerization reaction It is possible to appropriately perform the process.

The physical property value of the colored curable composition of the present invention used in the ink jet method is not particularly limited as long as it can be discharged by an ink jet head, but the viscosity at the time of discharge is 2 to 30 mPa · s from the viewpoint of stable discharge. It is preferably 2 to 20 mPa · s. Moreover, when ejecting with an apparatus, it is preferable to maintain the temperature of the inkjet ink at a substantially constant temperature in the range of 20 to 80 ° C. If the temperature of the device is set to a high temperature, the viscosity of the ink decreases and it becomes possible to eject higher viscosity ink. However, due to the increase in temperature, the ink is denatured by heat and the thermal polymerization reaction occurs in the head. The temperature of the apparatus is preferably in the range of 20 to 80 ° C. because the solvent evaporates on the surface of the nozzle that ejects ink or nozzle clogging easily occurs.
The viscosity is measured by using a commonly used E-type viscometer (for example, an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.) with the inkjet ink held at 25 ° C. Value.

  In addition, the surface tension (static surface tension) at 25 ° C. of the colored curable composition of the present invention used in the inkjet method is 20 to 40 mN in terms of improving wettability with respect to a non-permeable substrate and discharging stability. / M is preferable, and 20 to 35 mN / m is more preferable. Moreover, when discharging with an apparatus, it is preferable to maintain the temperature of the ink for inkjet in the range of 20-80 degreeC, and it is preferable to make the surface tension at that time into 20-40 mN / m. In order to keep the temperature of the inkjet ink constant with a predetermined accuracy, the ink temperature detecting means, the ink heating or cooling means, and the control means for controlling the heating or cooling according to the detected ink temperature are provided. It is preferable to use an apparatus. Alternatively, it is also preferable to have a means for reducing the influence on the ink physical property change by controlling the energy applied to the means for ejecting ink according to the ink temperature.

  The above-mentioned surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter FACE SURFACE TENSIOMETER CBVB-A3), 60% liquid temperature. It is a value measured by RH.

  Moreover, in order to maintain appropriately the shape which the colored curable composition of this invention wets and spreads after board | substrate landing, it is preferable to hold | maintain the liquid physical property of the colored curable composition after landing to a board | substrate predetermined. For this purpose, it is preferable to keep the substrate and / or the vicinity of the substrate within a predetermined temperature range. Alternatively, it is also effective to reduce the influence of temperature change by increasing the heat capacity of the table that supports the substrate.

  When the colored curable composition of the present invention is used for production of a color filter by an ink jet method, it is excellent in ink storage stability and suppresses aggregation and decomposition of the ink. Also, during continuous and intermittent discharge, it is difficult for discharge disturbance such as flying bend and non-discharge, excellent discharge stability, recovery after a certain period of rest, non-discharge etc. Excellent recoverability.

  A method for producing a color filter by the ink jet method using the colored curable composition of the present invention is not particularly limited. For example, the method described in paragraphs [0114] to [0128] of JP-A-2008-250188 is used. Can be used.

<Use of the color filter of the present invention>
The color filter of the present invention may further have an indium tin oxide (ITO) layer as a transparent conductive film. Examples of the ITO layer forming method include in-line low-temperature sputtering method, in-line high-temperature sputtering method, batch-type low-temperature sputtering method, batch-type high-temperature sputtering method, vacuum deposition method, and plasma CVD method. In order to reduce damage, a low-temperature sputtering method is preferably used.

  The color filter of the present invention is not particularly limited, for example, for liquid crystal displays, organic EL displays, liquid crystal projectors, portable terminals such as game machines and mobile phones, image display devices such as digital cameras and car navigation systems, and particularly for color image display applications. Applicable to. Further, it can be suitably used as a color filter for a solid-state imaging device such as a CCD image sensor or a CMOS image sensor used in a digital camera, a digital video camera, an endoscope, a mobile phone, or the like. Particularly, it is suitable for a high-resolution CCD element or CMOS element exceeding 1 million pixels.

The configuration of the solid-state imaging device is not limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
That is, it has a structure in which a transfer electrode made of a photodiode and polysilicon constituting a light receiving area is provided on a support, a color filter layer is provided, and then a microlens is laminated.
The camera system provided with the color filter of the present invention is provided with a camera lens, a cover glass on which an IR cut film is dichroically coated, a microlens, and the like from the viewpoint of light fading of the color material. It is desirable to absorb part or all of UV light of 400 nm or less. Also, the structure of the camera system is preferably such that the oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the colorant. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

  As described above, the colored curable composition, the color filter and the manufacturing method thereof, and the display and solid-state imaging device using the same have been described in detail with reference to various embodiments. Of course, various improvements and modifications may be made without departing from the scope of the present invention.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

(Preparation of pigment dispersion P1)
C. I. Pigment Blue PB15: 6 10 parts by weight, 4 parts by weight of Solsperse 24000GR as a dispersion resin, 50 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter), pigment A dispersion was prepared.

(Preparation of pigment dispersion P2)
C. I. Pigment Blue PB15: 6 9.5 parts by mass, C.I. I. Pigment Violet PV23 0.5 parts by mass, Solsperse 24000GR 4 parts by mass as a dispersion resin, 50 parts by mass of propylene glycol monomethyl ether acetate as a solvent are added, mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter), pigment A dispersion was prepared.

[Example 1]
(1) Preparation of resist solution A (negative type)
Propylene glycol monomethyl ether acetate 5.20 parts Cyclohexanone 52.6 parts Binder 30.5 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) (molar ratio = 60: 20: 20) ) Average molecular weight 30200 (polystyrene conversion), 41% cyclohexanone solution, dipentaerythritol hexaacrylate 10.2 parts, polymerization inhibitor (p-methoxyphenol) 0.006 parts, fluorosurfactant (trade name: F-475 0.80 parts Photopolymerization initiator: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (manufactured by TAZ-107 Midori Chemical Co., Ltd.) 0.58 Parts were mixed and dissolved to prepare a resist solution A.

(2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). Next, the resist solution A obtained in the above (1) was applied on a glass substrate washed with a spin coater so that the film thickness after drying was 2 μm, and dried by heating at 220 ° C. for 1 hour, with an undercoat layer. A glass substrate was prepared.

(3) Preparation of colored curable composition-150 parts by weight of pigment dispersion P1 or P2-80 parts of propylene glycol monomethyl ether acetate-Polymerizable compound: 14.0 parts of dipentaerythritol hexaacrylate-Polymerization inhibitor: p-methoxy 0.006 parts of phenol / fluorine-based surfactant (trade name: F-475, manufactured by DIC Corporation) 0.80 parts / photopolymerization initiator (trade name: Irgacure OXE-01, manufactured by Ciba Specialty Chemicals) 2.0 parts and (A) specific resin 40.0 parts of exemplary resins shown in Table 2 were mixed and dissolved to prepare a colored curable composition. In addition, the example resin number of (A) specific resin shown in Table 2 shows the number of the example resin described in the said Table 1.

(4) Exposure and development of colored curable composition (image formation)
(4-1) Coating film formation The thickness of the colored curable composition obtained in (3) above after drying on the undercoat layer of the glass substrate with an undercoat layer obtained in (2) above is 0.6 μm. Then, it was applied using a spin coater and pre-baked at 100 ° C. for 120 seconds.

(4-2) Pattern formation Next, using an exposure apparatus UX3100-SR (manufactured by Ushio Electric Co., Ltd.), the coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm with an exposure amount of 200 mJ / cm 2. . After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes.
As described above, a pattern suitable for red constituting the color filter was obtained.

(5) Evaluation The coating property of the coating film coated on the glass substrate formed in (4-1) and the pattern shape formed in the pattern in (4-2) were evaluated as follows. The evaluation results are shown in Table 2 below.

[Applicability]
The coating property of the coating film formed in (4-1) was judged with the naked eye.
-Criteria-
○: No problem in the surface shape ×: Abnormalities such as slits or unevenness occurred in the surface shape

[Pattern shape]
The development pattern of the various coating films after post-baking obtained in (4-2) above is observed with an optical microscope (Olympus Digital Microscope RX-20), and whether a fine pattern can be created or not is as follows. Evaluation was made according to the criteria.
-Criteria-
○: A fine pattern is produced.
Δ: The pattern is produced, but the pattern wrinkles are not fine.
X: A pattern cannot be produced.

〔Color unevenness〕
Analyzing the image taken with the microscope MX-50 (manufactured by Olympus) for the coating formed in (4-1) above, the percentage of pixels whose deviation from the average in color density is within ± 5% (percentage) Was calculated. The higher this value, the smaller the color unevenness and the better.

(Comparative Examples 1 and 2)
Evaluation similar to the said Example was performed except having changed the said specific resin into the following resin (Z-1) and (Z-2).

The composition ratios and molecular weights of the resins (Z-1) and (Z-2) are as follows.
(Z-1): Composition ratio (weight ratio, 80/20 from the left), Mw = 18,000
(Z-2): Composition ratio (weight ratio, 80/20 from the left), Mw = 17,000

  As can be seen from Table 2, it can be seen that, in the example, color unevenness is suppressed and coating properties and pattern formability are excellent as compared with the comparative example.

Claims (12)

(A) a resin having a repeating unit represented by the general formula (a) and a repeating unit represented by the general formula (b), (B) a pigment dispersion, (C) a photopolymerization initiator, (D ) A polymerizable curable composition containing a polymerizable compound.



[In General Formula (a), X ¹ represents a polymer main chain. Y ¹ represents a single bond or a divalent linking group. Q represents a phthalocyanine dye residue or a dipyrromethene dye residue. ]



[In the general formula (b), X ² represents a polymer main chain represented by any of the following formulas (X ¹ -1) to (X ¹ -12) . Y ² represents a divalent linking group represented by the following general formula (b ′) . Z represents an alkali-soluble group. ]


[In General Formula (b ′), A represents an alkylene group, a cycloalkylene group, or an arylene group. B is _{-CO 2 -, - O 2 C} -, - O -, - NH -, - representing the S-. C represents an alkylene group, a cycloalkylene group, or an arylene group. n represents an integer of 0 to 10. ]   X in the general formula (a) ¹ And X in the general formula (b) ² Each independently represents the formula (X ¹ -1) or (X ¹ The colored curable composition according to claim 1, which represents a polymer main chain represented by -2).   Z in the general formula (b) is -CO. ₂ The colored curable composition according to claim 1 or 2, which represents H.   The coloring according to any one of claims 1 to 3, wherein a ratio of the repeating unit represented by the general formula (b) to the whole (A) resin is 5% by mass or more and 60% by mass or less. Curable composition. The colored curable composition according to any one of claims 1 to 4, wherein the pigment contained in the (B) pigment dispersion is a pigment selected from a blue pigment, a violet color pigment, and a mixture thereof. object. A color filter provided with the coloring pattern which uses the colored curable composition of any one of Claims 1-5 . A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of claims 1 to 5 on a support, and exposing the colored layer in a pattern. A method for producing a color filter, comprising: an exposure step; and a development step of developing the colored layer after the exposure to form a colored pattern. The manufacturing method of the color filter of Claim 7 including the ultraviolet irradiation process which irradiates an ultraviolet-ray to the said coloring pattern formed by the said image development process. A solid-state imaging device comprising the color filter according to claim 6 . An image display device comprising the color filter according to claim 6 . A liquid crystal display comprising the color filter according to claim 6 . An organic EL display comprising the color filter according to claim 6 .