TW201624115A - Colored curable composition, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device - Google Patents

Abstract

This colored curable composition contains a coloring agent A that has a structure represented by formula (1), a curable compound and an organic solvent; and the coloring agent A is dispersed in the organic solvent. In the formula, each of R1-R10 independently represents a hydrogen atom, an alkyl group or the like; and R11 represents a sulfonate group or a bis(sulfonyl)imide group.

Description

Coloring curable composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and image display device

The present invention relates to a color hardening composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device.

In recent years, demand for solid-state imaging elements such as charge coupled device (CCD) image sensors has increased significantly due to the spread of digital cameras, camera-equipped mobile phones, and the like. As a main device of such a display or an optical element, a color filter is used, and the demand for further high sensitivity and miniaturization is improved. Such a color filter usually has red (R), green (G), and blue (B). The color patterns of the three primary colors function to decompose the transmitted light into three primary colors.

For example, Patent Literatures 1 to 3 describe the production of a color filter using an organic solvent-based colored curable composition containing a xanthene dye.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-235257

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-207158

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-61619

In the organic solvent-based coloring curable composition used for a color filter or the like, it is required to form a cured film having a small spectral variation before and after development and excellent light resistance.

For example, as a characteristic of a color filter, light resistance is an important subject, and a color filter can be made not only when the stability of the coloring agent with respect to light is low, but also when the stability of other materials with respect to light is low. The spectroscopic change. As a result of various studies on xanthene pigments, the present inventors have a tendency to have low light resistance by N-alkylated xanthene. For example, in the case of using an amine-containing dispersant, it is known that the dispersant is used. The color generated by the decomposition tends to cause a change in the spectral light that causes the loss of the blue splitting.

Further, in Patent Literatures 1 to 3, a color-curable composition in which a xanthene pigment is dispersed in an organic solvent is disclosed. However, in the color hardening composition disclosed in Patent Documents 1 to 3, according to the study of the present inventors, The dispersibility of the ton dye was poor, and as a result, it was found that xanthene pigment was dissolved in the developer, and fading was likely to occur after development, and the spectral shift before and after development was large. Further, it is known that light resistance is also poor.

The present invention has been made in view of such circumstances, and an object of the invention is to provide a color-curable composition capable of forming a film having a small spectral variation before and after development and having excellent light resistance. Further, an object of the invention is to provide a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state image sensor, and an image display device.

As a result of a detailed study, the present inventors have found that the above object can be attained by using a colored curable composition containing a structure represented by the formula (1) described later. The xanthene compound, that is, the colorant A, the curable compound, and the organic solvent, and the colorant A is dispersed in an organic solvent. The present invention provides the following.

<1> A colored curable composition comprising a coloring agent A having a structure represented by the following formula (1), a curable compound, and an organic solvent, and the coloring agent A is dispersed in an organic solvent;

[Chemical Formula 1]

In the formula, R ¹ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 or -NHSO ₂ R ^X1 ,

R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group or an aryl group.

R ¹¹ represents a sulfonic acid group or a bis(sulfonyl) fluorenylene group.

<2> The colored curable composition according to <1>, wherein, in the colorant A, R ¹ , R ⁵ , R ⁶ and R ¹⁰ in the formula (1) are each independently an alkyl group.

<3> The colored curable composition according to <1>, wherein, in the colorant A, R ¹ , R ⁵ , R ⁶ and R ^{10 of the} formula (1) are each independently a methyl group, an ethyl group or Isopropyl.

In the coloring agent A, R ¹¹ of the formula (1) is a sulfonic acid group, and R ² and R ^{3 are} , in the coloring agent A, the colored curing composition according to any one of the above-mentioned items. R ⁴ , R ⁷ , R ⁸ and R ⁹ are a hydrogen atom.

The colored curable composition according to any one of <1> to <4>, wherein the organic solvent is at least one selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent.

The colored curing composition according to any one of the above aspects, further comprising a photopolymerization initiator, wherein the curable compound is a radical polymerizable compound.

The colored curable composition as described in any one of <1> to <6> further containing an acidic dispersing agent having an acid value of 30 mgKOH/g or more.

<8> The colored curable composition as described in <7>, which contains two or more types of acidic dispersing agents.

The colored hardening composition as described in any one of <1> to <8> which further contains the pigment which has a phthalocyanine skeleton.

The colored curable composition as described in any one of <1> to <9> which further contains a dye as a coloring agent other than the coloring agent A.

<11> The colored curable composition according to <10>, wherein the dye is a dye having a skeleton selected from the group consisting of phthalocyanine, triarylmethane, and pyrromethene.

<12> The colored curable composition according to any one of <1> to <11> which is used for a color filter.

<13> A color filter which is formed using the colored curable composition according to any one of <1> to <12>.

<14> A pattern forming method comprising the step of forming a colored curable composition layer on a support by using the colored curable composition according to any one of <1> to <12>; The composition layer is exposed in a pattern; and the unexposed portion is removed by development to form a colored pattern.

<15> A method of producing a color filter, comprising the pattern forming method described in <14>.

<16> A solid-state image sensor having the color filter described in <13> or a color filter obtained by the method for producing a color filter according to <15>.

<17> An image display device comprising the color filter described in <13> or a color filter obtained by the method for producing a color filter according to <15>.

According to the present invention, it is possible to provide a color-curable composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and a pattern capable of forming a film having a small spectral variation before and after development and having excellent light resistance. Like a display device.

Hereinafter, the contents of the present invention will be described in detail.

In the label of the group (atomic group) in the present specification, the label which is not labeled and unsubstituted includes those having no substituent and having a substituent. For example, "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, light means active light or radiation. Further, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like.

The "exposure" in the present specification means not only the bright line spectrum of a mercury lamp, but also the exposure of far ultraviolet rays, X-rays, EUV light, etc. represented by excimer lasers, electron beams, ion beams, etc., unless otherwise specified. The painting of the particle beam is also included in the exposure.

In the present specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the overall composition of the colored curable composition.

In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group.

In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in the polymerization reaction.

In the present specification, "the terminology of the step includes not only the independent steps but also the term as long as it can clearly exhibit the desired effect of the steps, even if it cannot be clearly distinguished from the other steps.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, and iPr represents an isopropyl group.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC).

In the present specification, a pigment means an insoluble pigment compound which is not easily dissolved in a solvent. It is typical that the pigment exists in a state of being dispersed in an organic solvent. Here, the solvent may be any solvent, and examples thereof include a solvent exemplified in the solvent column described later. The pigment used in the present invention is preferably, for example, a dissolved amount of 100 g of propylene glycol monomethyl ether acetate at 23 ° C and a dissolved amount of 100 g with respect to water at 23 ° C of 0.1 g or less.

In the present specification, a dye means a dye compound which is easily dissolved in a solvent. It is typical that the dye exists in a state in which the pigment compound is dissolved in the composition. Here, the solvent may be any solvent, and examples thereof include a solvent exemplified in a solvent column to be described later. The dye used in the present invention is preferably dissolved in an amount of more than 2.0 g per 100 g of propylene glycol monomethyl ether acetate at 23 ° C.

In the present specification, the repeating unit ratio in the compound having a repeating unit means a molar ratio unless otherwise specified.

<Coloring hardenable composition>

The colored curable composition of the present invention contains a coloring agent A having a structure represented by the formula (1) to be described later, a curable compound, and an organic solvent, and the coloring agent A is dispersed in an organic solvent.

Since the coloring agent A is a solid and has low solubility with respect to an organic solvent, it is possible to suppress fading after development, and it is possible to manufacture a color filter having a small variation in spectral light before and after development. Further, by using the colored curable composition of the present invention, a color filter excellent in light resistance can be formed.

In addition, since the coloring agent A is dispersed in the organic solvent, the coloring agent A of the present invention can suppress precipitation, aggregation, and the like of the coloring agent, and is excellent in dispersion stability. Further, since the colorant A is hard to be thermally dispersed, it is possible to form a color filter excellent in heat resistance.

Further, in the present invention, the "dispersion of the colorant A in the organic solvent" means that the particles of the colorant A exist in a state of floating or suspended in the organic solvent. The colorant A is dispersed in an organic solvent, and can be confirmed, for example, by particle size distribution measurement using a dynamic light scattering method.

Hereinafter, the present invention will be described in detail.

<<Coloring agent A>>

The color hardening composition of the present invention contains the coloring agent A having a structure represented by the following formula (1).

[Chemical Formula 2]

R ¹ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 or -NHSO ₂ R ^X1 ,

R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group or an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, and a straight chain or a branched chain is preferred. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and more preferably a methyl group, an ethyl group or an isopropyl group.

The aryl group may be a single ring or a polycyclic ring. The aryl group has preferably 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may also contain a hetero atom. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

In the formula (1), R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , R ⁵ and R ¹⁰ are preferably the same group.

R ¹ , R ⁵ , R ⁶ and R ¹⁰ are preferably an alkyl group. R ¹ , R ⁵ , R ⁶ and R ¹⁰ are each independently preferably a methyl group, an ethyl group or an isopropyl group. According to this aspect, the effect of reducing the solubility of the solvent can be obtained.

It is preferred that R ² and R ⁷ are a hydrogen atom.

R ³ and R ⁸ are each independently a hydrogen atom or an alkyl group, and a hydrogen atom is more preferable.

R ⁴ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 or -NHSO ₂ R ^X1 are preferred, and a hydrogen atom is more preferred.

In the present invention, R ² , R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are preferably a hydrogen atom. According to this aspect, the effect of improving the absorbance per unit mass can be obtained.

R ¹¹ represents a sulfonic acid group or a bis(sulfonyl) fluorenylene group. A sulfonic acid group is preferred from the viewpoint of reducing solvent solubility.

The bis(sulfonyl) fluorenylene imino group is a group represented by the following formula (AN-1).

[Chemical Formula 3]

In the formula, R ¹⁰⁰ represents a halogen atom, an alkyl group or an aryl group.

It is preferred that the halogen atom is a fluorine atom.

The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group is preferably a straight chain or a branched chain, and a straight chain is more preferred. It is preferred that a part of hydrogen atoms in the alkyl group are substituted by a fluorine atom, and it is more preferable that all hydrogen atoms are replaced by a fluorine atom. The alkyl group represented by R ¹⁰⁰ is preferably an alkyl group (perfluoroalkyl group) in which all hydrogen atoms are substituted by a fluorine atom and has 1 to 10 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms is further preferably used. Trifluoromethyl is especially preferred.

The aryl group has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryl group may have a substituent. The substituent may, for example, be a halogen atom, an alkyl group, an alkoxy group, a carbonyl group, a carbonyloxy group, an aminomethylcarbonyl group, a sulfo group, a sulfonylamino group or a nitro group, and a halogen atom or an alkyl group is preferred. A fluorine atom or an alkyl group is more preferable.

Further, in the compound represented by the formula (1), the cation is present as follows without delocalization, and the following structures have the same meanings and are included in the inventors.

[Chemical Formula 4]

In the present invention, the colorant A is preferably a structure represented by the following formula (1a), and is more preferably represented by the following formula (1b).

[Chemical Formula 5]

In the above formula, R ¹ to R ¹¹ have the same meanings as those described in the formula (1), and the preferred ranges are also the same.

The colorant A preferably has a molecular weight of from 500 to 900, more preferably from 550 to 800. The molecular weight of the colorant A is a theoretical value obtained from the structural formula.

Specific examples of the colorant A include the following.

[Chemical Formula 6]

In the present invention, the solubility of the colorant A with respect to the organic solvent is preferably small. Specifically, the amount of the colorant A dissolved in 100 g of propylene glycol monomethyl ether acetate at 23 ° C, the amount of the colorant A dissolved in 100 g of cyclohexanone at 23 ° C, and the ring of the coloring agent A with respect to 23 ° C Any one of the amounts of the pentanone 100 g dissolved is preferably 1 g or less, and the amount of the colorant A dissolved in each organic solvent is preferably 1 g or less.

In the present invention, it is preferred that the coloring agent A is fine and granulated. As a method of refining the coloring agent A, for example, a liquid composition having a high viscosity is prepared by using a coloring agent A, an organic solvent, and a water-soluble inorganic salt, and is ground by applying a stress using a wet pulverizing apparatus or the like. Method, etc.

The organic solvent mentioned later can be mentioned as an organic solvent. The amount of the organic solvent used in the refining step is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the coloring agent A.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate. The amount of the water-soluble inorganic salt to be used in the refining step is preferably 1 to 50 parts by mass, more preferably 1 to 10 parts by mass, per part by mass of the coloring agent A. Further, a water-soluble inorganic salt having a water content of 1% or less is preferably used.

The operating conditions of the wet pulverizing apparatus in the miniaturization step of the coloring agent A are not particularly limited, and in order to efficiently perform the grinding by the pulverizing medium, the operating conditions when the apparatus is a kneading machine are the blades in the apparatus. The rotation speed is preferably from 10 to 200 rpm, and the two-axis rotation ratio is relatively large, and the grinding effect is large and preferable. The running time in combination with the dry pulverization time is preferably from 1 to 8 hours, and the internal temperature of the apparatus is preferably from 50 to 150 °C. Further, the water-soluble inorganic salt as the pulverization medium has a pulverized particle size of 5 to 50 μm, a narrow particle diameter distribution, and a spherical shape.

In the color hardening composition of the present invention, the coloring agent A is preferably present as particles in the composition. In particular, the average particle diameter (r) of the colorant A satisfies 20 nm ≤ r ≤ 300 nm, preferably 25 nm ≤ r ≤ 250 nm, and more preferably 30 nm ≤ r ≤ 200 nm. When the average particle diameter (r) of the colorant A is within the above range, a color filter having high contrast and high light transmittance can be obtained. The "average particle diameter" as used herein means the average particle diameter of secondary particles in which primary particles (single crystallites) of the colorant A are aggregated. The average particle diameter can be determined by scanning with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring the size of 100 particles in a portion where the particles are not aggregated, and calculating an average value.

Further, in the particle size distribution of the secondary particles of the coloring agent A (hereinafter simply referred to as "particle size distribution") which can be used in the present invention, it is desirable that the secondary particles in the (average particle diameter ± 100) nm are integral. 70% by mass or more and 80% by mass or more are preferable. Further, in the present invention, the particle size distribution is measured by the scattering intensity distribution.

In the colored curable composition of the present invention, the content of the coloring agent A relative to the total solid content of the colored curable composition is preferably from 10 to 80% by mass. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

Further, the content of the coloring agent A in the total amount of the colorant is preferably from 30 to 100% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.

The coloring agent A can be one type. Further, R ¹ to R ^{11 in the} above formula (1) may be a compound containing two or more different combinations. When two or more types are contained, the total amount is preferably in the above range.

<<Other coloring agents>>

The colored curable composition of the present invention may contain a coloring agent other than the above-mentioned coloring agent A, and it is preferable to contain other coloring agents. Other colorants may be any of a dye and a pigment, or both may be used in combination. The other coloring agents may be used alone or in combination of two or more.

Examples of the pigment include various conventional inorganic pigments or organic pigments. Further, in the case of an inorganic pigment or an organic pigment, in consideration of a high transmittance, it is preferred to use a pigment having a small average particle diameter as much as possible, and in consideration of handleability, the average particle diameter of the pigment is It is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

Examples of the inorganic pigment include a metal compound represented by a metal oxide, a metal salt or the like, and specific examples thereof include black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, and titanium. a metal oxide such as magnesium, chromium, zinc or bismuth and a composite oxide of the above metals.

In the present invention, the following organic pigments can be preferably used. However, the present invention is not limited to these.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34 , 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86 , 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128 , 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 , 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Wait,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279

C.I. Pigment Green 7, 10, 36, 37, 58

C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42

C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80

C.I. Pigment Black 1

These organic pigments can be used singly or in combination with various pigments in order to improve color purity.

Among them, a pigment having a phthalocyanine skeleton (also referred to as a phthalocyanine pigment) is preferred, and C.I. Pigment Blue 15:6 is more preferred.

For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and JP-A No. 2592207 can be used. , U.S. Patent No. 4,808, 051, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 595, 950, U.S. Patent No. 5,567, 920, Japanese Patent Application Laid-Open No. Hei No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, No. 6-51115 A pigment in the publication of Japanese Laid-Open Patent Publication No. Hei 6-194928. If it is distinguished as a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxophthalocyanine compound, or a pyrazole can be used. A triazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, a dye polymer can also be used as the dye. The compound described in JP-A-2011-213925, and JP-A-2013-041097 can be mentioned as a pigment.

In the present invention, the dye is preferably a dye having a skeleton selected from the group consisting of phthalocyanine, triarylmethane and pyrromethylene, and a dye having a phthalocyanine skeleton or a triarylmethane skeleton is more preferable, and a dye having a phthalocyanine skeleton. Further preferred. By containing these dyes, the dispersibility of the above-mentioned coloring agent A can be improved in the composition. In addition, heat resistance and light resistance are improved.

The dye having a phthalocyanine skeleton (also referred to as a phthalocyanine dye) may, for example, be a compound represented by the following formula (F).

Formula (F)

[Chemical Formula 7]

In the formula (F), M ¹ represents a metal atom or a metal compound. Examples of the metal atom or the metal compound include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, metal atoms such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , Metal chloride such as GeCl ₂ , metal oxide such as TiO or VO, or metal hydroxide such as Si(OH) ₂ . In particular, Cu is preferred.

Rp ₁ to Rp ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₃ M ² , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1 or -SO ₂ NR ^X1 R ^X2 ,R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and M ² may be a quaternary ammonium cation, a monovalent metal atom such as sodium, lithium or potassium, or a divalent metal atom such as Mg or Ca. Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and the like. From the viewpoint of excellent spectroscopicity, a compound represented by the following formula (F-1) is particularly preferable.

Formula (F-1)

[Chemical Formula 8]

In the formula (F-1), M ¹ represents a metal atom or a metal compound. The same meaning as M ¹ M Department of formula (F-1) ¹ and the formula (F), the preferred range is also the same.

In the formula (F-1), R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, or an aryl group.

The alkyl group represented by R ^a and R ^b preferably has 1 to 10 carbon atoms. It is preferred that the alkyl group be a straight chain or a branched chain. The alkyl group may be unsubstituted or may have a substituent. The substituent may, for example, be an aryl group, an alkoxy group, an allyloxy group, an aryloxy group or a halogen atom.

The aryl group represented by R ^a and R ^b may be a single ring or a polycyclic ring. The number of carbon atoms is preferably 6 to 25, more preferably 6 to 15, and even more preferably 6 to 12. The aryl group may contain a hetero atom. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The aryl group may be unsubstituted or may have a substituent. The substituent may, for example, be an alkyl group, an alkoxy group, an allyloxy group or a halogen atom.

In the formula (F-1), X may be an acid group such as a carboxyl group or a sulfo group or a salt thereof. Examples of the atom or atomic group constituting the salt include a metal atom such as lithium, sodium or potassium, and a quaternary ammonium salt such as tetrabutylammonium.

n represents an integer of 1 to 10, and 1 to 5 is preferred.

a, b, and c each independently represent 0 to 8, and at least one of a and b is 1 or more, and the total of a, b, and c is 1 to 8.

Specific examples of the phthalocyanine dye include the following compounds, and the compounds described in paragraphs 0044 to 0059 of WO2009/119364 pamphlet.

[Chemical Formula 9]

The dye having a triarylmethane skeleton (also referred to as a triarylmethane dye) may, for example, be a compound represented by the following formula (TP).

Formula (TP)

[Chemical Formula 10]

In the formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b, and c represent integers from 0 to 4. When a, b, and c are 2 or more, Rtp ⁶ , Rtp ^{7 ,} and Rtp ⁸ may be bonded to each other to form a ring. X ^- represents an anionic structure.

In the formula (TP), the anion structure represented by X ^- is selected from the group consisting of a sulfonic acid anion, a carboxylic acid anion, a sulfonimide anion, a bis(alkylsulfonyl) quinone imine anion, and a tris(alkylsulfonate). yl) methide anion, carboxylate anion, tetraarylborate ^{anion, -CON - CO -, - CON} - SO 2 -, BF 4 -, PF 6 -, SbF 6 -, B - (CN) 3 OCH 3 At least one of them is preferred. Selected from a sulfonate anion, a sulfonium imide anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl)methide anion, a carboxylate anion, a tetraarylborate anion, BF ₄ ^- at least one of PF ₆ ^- and SbF ₆ ^- is more preferred.

In the formula (TP), Rtp ¹ to Rtp ⁶ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ⁵ is preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , and NRtp ⁹ Rtp ¹⁰ is particularly preferred.

In the formula (TP), Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a phenyl group.

In the formula (TP), Rtp ⁶ , Rtp ⁷ and Rtp ⁸ are a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and 6 to 15 carbon atoms. The aryl group, the carboxyl group or the sulfo group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group or a carboxyl group. Rtp ⁶ and Rtp ⁸ are preferably an alkyl group having 1 to 5 carbon atoms, Rtp ⁷ is an alkenyl group (in particular, a phenyl group in which two adjacent alkenyl groups are bonded is preferred), and a phenyl group or a carboxyl group is preferred. good.

In the formula (TP), a, b or c each independently represents an integer of 0 to 4. Preferably, a and b are 0 or 1 respectively, and c is an integer of 0 to 2, preferably.

Specific examples of the triarylmethane dye include the following compounds, and the compounds described in paragraphs 0176 to 0177 of JP-A-2014-186342.

[Chemical Formula 11]

The dye having a pyrrolethymethylene skeleton (also referred to as a pyrromethene dye) may, for example, be a compound represented by the following formula (PM).

Formula (PM)

[Chemical Formula 12]

R ¹¹ and R ¹⁶ each independently represent an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamine group. R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group or an aryl group, and an alkyl group, an alkenyl group or an aryl group is further preferred, and an alkyl group is particularly preferred.

R ¹² to R ¹⁵ each independently represent a hydrogen atom or a substituent.

In R ¹² to R ¹⁵ , R ¹² and R ¹⁵ are alkoxycarbonyl, aryloxycarbonyl, aminomethylindenyl, alkylsulfonyl, arylsulfonyl, nitrile, imine or amine Further, a mercaptosulfonyl group is preferred, and an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethylcarbonyl group, an alkylsulfonyl group, a nitrile group, an imido group, an amine formylsulfonyl group is more preferred, and an alkoxy group is preferred. A carbonyl group, an aryloxycarbonyl group, an aminomethylguanidinyl group, a nitrile group, an imido group, an amine formylsulfonyl group is further preferred.

Among R ¹² to R ¹⁵ , R ¹³ and R ¹⁴ are preferably an alkyl group or an aryl group.

R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. It is preferred that R ¹⁷ is a hydrogen atom.

Ma represents a metal atom or a metal compound. The metal atom or the metal compound is exemplified in the formula (F), and Zn, Cu, Co or V=O is preferable, and Zn is more preferable.

X ² and X ³ each independently represent NR ^x (R ^x represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom, an oxygen atom or sulfur atom. It is preferred that X ² and X ³ are oxygen atoms.

Y ¹ and Y ² each independently represent NR ^y (R ^y represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom or a carbon atom. R ¹¹ and Y ¹ may be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R ¹⁶ and Y ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members. Y ¹ is NH, and Y ² is preferably a nitrogen atom.

X ¹ represents a group which can be bonded to Ma. X ¹ may be any ^one as long as it can bond to Ma, and specific examples thereof include water, an alcohol (for example, methanol, ethanol, or propanol), and the like, and a "metal chelate compound" ( [1] Compounds described in Shoukou Wuyi, Ueno Jingping (1995 Nanjiangtang); [2] (1996); [3] (1997), etc.). Among them, water, a carboxylic acid compound, and an alcohol are preferable from the viewpoint of production, and water or a carboxylic acid compound is more preferable.

a represents an integer of 0 to 2, and 0 or 1 is preferred.

Examples of the pyrrolethymethylene dye include the following compounds, and the compounds described in paragraphs 0100 to 0102 of JP-A-2014-186342.

[Chemical Formula 13]

When the coloring-curable composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably 0.1 to 20 parts by mass, and 0.1 to 15 parts by mass, per 100 parts by mass of the coloring agent A. Preferably, 0.1 to 10 parts by mass is further preferred.

Further, the content of the phthalocyanine pigment is preferably from 80 to 300 parts by mass, more preferably from 90 to 250 parts by mass, even more preferably from 100 to 200 parts by mass, per 100 parts by mass of the color former A. If it is the above range, the effect of excellent spectroscopicity can be obtained. In addition, the phthalocyanine pigment may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to add up to the above range.

Further, the content of the dye is preferably 1 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, per 100 parts by mass of the coloring agent A. When the content of the dye is in the above range, the dispersibility of the colorant A is improved, and the dispersion stability of the colored curable composition is further improved. Further, the dye may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to add up to the above range.

In the colored curable composition of the present invention, the content of the colorant with respect to the total solid content in the colored curable composition is preferably from 10 to 90% by mass. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.

<<Cure compound>>

The colored curable composition of the present invention contains a curable compound. As the curable compound, a known compound which can be crosslinked by a radical, an acid or heat can be used. For example, a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group can be given. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group.

In the present invention, the curable compound is preferably a radically polymerizable compound.

In the present invention, the radically polymerizable compound (hereinafter also referred to as a polymerizable compound) may be, for example, a monomer or a prepolymer, that is, may be a dimer, a trimer, and an oligomer, or a mixture thereof. And any of the chemical forms such as the multimers.

The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.

Examples of the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and the like. Such polymers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and such polymers. Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or an epoxy group may be suitably used, and A dehydration condensation reaction of a monofunctional or polyfunctional carboxylic acid or the like. Further, a reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol may be suitably used. And a reaction product of an unsaturated carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, a group of compounds in which the above unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether or an allyl ether can also be used.

As the specific compound, the compound described in Paragraph Nos. [0095] to [0108] of JP-A-2009-288705 can be suitably used in the present invention.

In the present invention, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable compound. As an example, for example, a compound described in paragraph 0227 of JP-A-2013-29760, and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents are incorporated in the specification of the present application. in.

The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.) or dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON KAYAKU CO.). , manufactured by LTD.) dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA) ; manufactured by NIPPON KAYAKU CO., LTD., manufactured by A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and the structure of the (meth)acryloyl group via ethylene glycol and propylene glycol residues ( For example, SR454, SR499, marketed by SARTOMER Company, Inc.). These types of oligomers can also be used. Further, KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.) can also be used.

The form of a preferred polymerizable compound is shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group polymerizability. More preferably, the compound is preferably an aliphatic polyhydroxy compound of the ester which is pentaerythritol and/or dipentaerythritol. For example, M-510, M-520, etc. which are polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD. can be mentioned as a commercial item.

The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH/g, more preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Further, the photopolymerization performance is good and the curability is excellent.

A compound having a caprolactone structure in the polymerizable compound is also a preferred state.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, which is ε-caprolactone. The modified polyfunctional (meth) acrylate can be obtained by using trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as pentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferred.

[Chemical Formula 14]

In the general formula (Z-1), all of the six R groups are groups represented by the following formula (Z-2), or one to five of the six R groups are represented by the following formula (Z-2). The group represented by the above is the group represented by the following formula (Z-3).

[Chemical Formula 15]

In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[Chemical Formula 16]

In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

A polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. CO., LTD. as KAYARAD DPCA series, and DPCA-20 (the above formula (Z-1) to (Z-3) can be mentioned. Wherein m = 1, the number of groups represented by the formula (Z-2) = 2, the compound in which all R ¹ are a hydrogen atom), DPCA-30 (the above formula (Z-1) to (Z-3) m = 1, the number of groups represented by the formula (Z-2) = 3, a compound in which all R ¹ are a hydrogen atom), and DPCA-60 (in the above formula (Z-1) to (Z-3)) m = 1, the number of the groups represented by the formula (Z-2) = 6, the compound in which all of R ¹ is a hydrogen atom), DPCA-120 (in the above formula (Z-1) to (Z-3), m = 2, the number of groups represented by the formula (Z-2) = 6, the compound in which all of R ¹ is a hydrogen atom), and the like.

As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can be used.

[Chemical Formula 17]

In the general formulae (Z-4) and (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group.

In the general formula (Z-4), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40.

In the general formula (Z-5), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferably.

Further, the total of each m is preferably an integer of from 2 to 40, more preferably from 2 to 16, more preferably an integer of from 4 to 8.

In the general formula (Z-5), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable.

Further, the total of n is preferably 3 to 60, the integer of 3 to 24 is more preferably, and the integer of 6 to 12 is more preferably.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferably It is a form in which the end of the oxygen atom side is bonded to X.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), it is preferred that all of the six X atoms are acrylonitrile groups.

In addition, the total content of the polymerizable compound of the compound represented by the formula (Z-4) or the formula (Z-5) is preferably 20% by mass or more, more preferably 50% by mass or more.

The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a conventionally known procedure: a ring-opening skeleton of ethylene oxide or propylene oxide by a ring-opening addition reaction a step of bonding to pentaerythritol or dipentaerythritol; and, for example, a step of introducing (meth)acrylonium chloride to a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and those skilled in the art can easily synthesize the compound represented by the formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are also more preferable.

Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. , (e), (f) are preferred.

[Chemical Formula 18]

[Chemical Formula 19]

As a commercial item of the polymerizable compound represented by the general formula (Z-4) or (Z-5), for example, a 4-functional acrylic acid having four ethyleneoxy chains manufactured by SARTOMER Company, Inc. Ester-SR-494, DPCA-60 of 6-functional acrylate having 6 pentyleneoxy chains manufactured by NIPPON KAYAKU CO., LTD., TPA of trifunctional acrylate having 3 isobutyleneoxy chains -330 and so on.

The urethane described in Japanese Patent Publication No. Hei 2-16765, and Japanese Patent Publication No. Hei 2-26765 The acrylate-based structure having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Amino acid compound is also preferred. In addition, it has an amine-based structure and a sulfide structure in the molecule, as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can be obtained as a color-curable composition having an excellent photospeed.

Commercially available products include urethane oligomer UAS-10, UAB-140 (made by SANYO-KOKUSAKU PULP CO., LTD.), and UA-7200 (SHIN-NAKAMURA CHEMICAL CO., LTD. ), DPHA-40H (manufactured by NIPPON KAYAKU CO., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CO., LTD.).

<<<Compound with epoxy group>>>

In the present invention, a compound having an epoxy group can be used as the curable compound.

In the case of patterning by dry etching, a compound having an epoxy group is preferably used as the curable compound.

As the compound having an epoxy group, it is preferred to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effects of the present invention can be exhibited more effectively. The epoxy group is preferably 2 to 10 in one molecule, more preferably 2 to 5, and particularly preferably 3.

The compound having an epoxy group in the present invention can preferably be used as a structure having two benzene rings bonded by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

Further, it is preferred that the epoxy group is connected via a linking group. The linking group may, for example, be an aryl group selected from an alkyl group, an arylene group, -O-, an alkyl group which may have a substituent, or an alkyl group which may have a substituent, represented by -NR'- (R' represents a hydrogen atom. A hydrogen atom is preferably a structure represented by at least one of -SO ₂ -, -CO-, -O-, and -S-.

The epoxy equivalent of the compound having an epoxy group (=the molecular weight of the compound having an epoxy group/the number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and 100 to 300 g/eq. Further preferred.

The compound having an epoxy group may be a low molecular compound (for example, having a molecular weight of less than 2,000, and further, a molecular weight of less than 1,000), or may be any one of a macromolecular compound (for example, a molecular weight of 1,000 or more, in the case of a polymer, The weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.

For the compound having an epoxy group, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraph numbers of JP-A-2014-089408 can be used. The compound described in 0085 to 0092. This is incorporated into the present specification.

As a commercial item, "EHPE3150, DAICEL CHEMICAL INDUSTRIES, CO., LTD.", "EPICLON N660 (made by DIC Corporation)", etc. are mentioned, for example.

In the colored curable composition of the present invention, the content of the curable compound is preferably from 0.1 to 40% by mass based on the total solid content of the colored curable composition. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, 30% by mass or less, more preferably 20% by mass or less. One type of the curable compound may be used alone or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably in the above range.

<<Multifunctional thiol compound>>

The colored curable composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly, a compound having a structure represented by the following formula (T1) is preferred.

General formula (T1)

[Chemical Formula 20]

(In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence.)

In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and an L-alkyl group having 2 to 12 carbon atoms is particularly preferred. . Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used singly or in combination of plural kinds.

[Chemical Formula 21]

In the case where the colored curable composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably 0.3 to 8.9% by mass, and preferably 0.8 to 6.4% by mass based on the total solid content of the colored curable composition. For better. Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<Organic solvent>>

The colored curable composition of the present invention contains an organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the coloring-curable composition. However, solubility, coating property, and safety of each of a coloring agent, a resin, and a curable compound are considered. It is better to make a choice. In particular, the organic solvent is preferably at least one selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent, from the viewpoint of the dispersibility of the coloring agent A. The organic solvent may be used singly or in combination of two or more. In the present invention, the "ether solvent" means a solvent containing an ether bond, the "ester solvent" means a solvent containing an ester bond, and the "ketone solvent" means a solvent containing a ketone bond. In other words, the alcohol-based solvent containing an ether bond is an ether solvent or an alcohol solvent, and the solvent having an ether bond and an ester bond is an "ether solvent" or an "ester solvent".

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, Cyclohexanol acetate, γ-butyrolactone, propylene glycol diacetate, 1,3-butylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether Acid ester, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, 2-ethoxypropane Methyl ester, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl Alkyl acetate, 3-methyl-3-methoxybutyl acetate, and the like.

Examples of the ether solvent include a solvent having an ether bond in the above ester solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Monoalkyl ethers; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single Propylene glycol monoalkyl ethers such as propyl ether and propylene glycol monobutyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Alkyl ether, phenethyl ether, methyl aniether and other phenol ethers; 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, and the like.

Examples of the ketone solvent include a solvent having a ketone bond in the above solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, and 4 - heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

Examples of the alcohol-based solvent include alcohols in the above solvents, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mm mpl/L or less, and more preferably no peroxide is contained.

In the present invention, the SP (Solubility Parameter) value of the organic solvent is preferably 15 to 25 (MPa) ^{1/2, more} preferably 19 to 23 (MPa) ^1/2 . In addition, the SP value is used in the present invention based on the value of the Hoy method. The literature of the Hoy method can be appropriately cited by HL Hoy: J. Paint Tech., 42 (540), 76-118 (1970) and SP value basis, application and calculation method (Yamamoto, consulting organization, 2005).

The content of the organic solvent is preferably from 5 to 80% by mass in terms of the total solid content concentration of the colored curable composition from the viewpoint of coatability. The lower limit is, for example, 5% by mass or more, more preferably 10% by mass or more. The upper limit is, for example, 60% by mass or less, more preferably 50% by mass or less.

The colored curable composition of the present invention may contain only one organic solvent, or may contain two or more organic solvents. When two or more types are contained, it is preferable that the total amount becomes the above range.

<<Resin>>

The colored curable composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing the colorant in the composition or the use of the binder. Further, a resin mainly used for dispersing a colorant such as a pigment is also referred to as a dispersant. However, such use of the resin is an example, and it may be used for the purpose other than the use.

In the colored curable composition of the present invention, the content of the resin is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, based on the total solid content of the colored curable composition. When the content of the resin is in the above range, the dispersibility of the colorant is good.

In the colored curable composition of the present invention, the content of the acidic resin is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, based on the total solid content of the colored curable composition. When the content of the acidic resin is in the above range, the developability is good.

In the colored curable composition of the present invention, the ratio of the acidic resin in the total mass of the resin is preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass, still more preferably from 70 to 100% by mass.

<<<Dispersant>>>

In the present invention, it is preferred that the colored curable composition contains a dispersing agent. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (basic resin).

The dispersant preferably contains at least an acidic dispersant, and more preferably an acidic dispersant. The dispersant can effectively suppress the generation of acicular foreign matter by containing at least an acidic dispersant. Further, the dispersibility of the colorant is improved, and unevenness in brightness is less likely to occur. Further, since excellent developability can be obtained, pattern formation can be appropriately performed by photolithography. In addition, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the acidic dispersant (acid resin) represents a resin having a larger amount of acid groups than the amount of the basic group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, the acidic dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more, substantially only A resin composed of an acid group is more preferable. The acid group of the acidic dispersant (acid resin) is preferably a carboxyl group.

Further, the alkaline dispersant (basic resin) means a resin having a larger amount of a basic group than the acid group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, it is preferred that the basic dispersant (basic resin) is a resin having a basic group content of 50 mol% or more. It is preferred that the basic group of the basic dispersant is an amine group.

The acid dispersant (acid resin) preferably has an acid value of 30 mgKOH/g or more, more preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and particularly preferably 60 to 105 mgKOH/g. In the present invention, the acid value means the number of mg of potassium hydroxide required to neutralize the acidic component per 1 g of the solid component.

In the present invention, the content of the dispersant is preferably from 100 to 500 parts by mass, more preferably from 150 to 400 parts by mass, per 100 parts by mass of the colorant A.

In the present invention, the dispersing agent may be used singly or in combination of two or more. When two or more types are used in combination, it is preferred to use two or more kinds of acidic dispersants in combination. According to this state, the dispersion stability of the composition can be improved.

The dispersing agent may, for example, be a polymer dispersing agent (for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester) And modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The polymer dispersant adsorbs on the surface of the pigment to prevent re-agglomeration. Therefore, as a preferable structure, the terminal modified type polymer, the graft type polymer, and the block type polymer which have an anchor part to the surface of a pigment are mentioned.

For example, JP-A-2002-273191 discloses a polymer having a phosphate group at a terminal, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-533455. The polymer having a sulfonic acid group at the terminal, and a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, and the like. Further, in the polymer terminal, two or more polymers which are anchored to the surface of the pigment (acid group, basic group, partial skeleton of organic dye or heterocyclic ring) are introduced into the polymer terminal, as described in JP-A-2007-277514. The dispersion stability is also excellent, so it is preferred.

The graft type polymer may, for example, be a polyester-based dispersant or the like. Specifically, poly(lower alkylene imine) and poly group described in JP-A-H05-370820, JP-A-H08-507960, JP-A-2009-258668, and the like. The reaction product of the polyallylamine and the polyester described in Japanese Laid-Open Patent Publication No. Hei 9-169821, and the like, and the publication of the International Publication No. 2004-37986 A copolymer of a macromonomer and a nitrogen atom monomer described in WO2010/110491, etc., as described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. A graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye; a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like; An inert resin having a basic group and an acid group.

As the macromonomer used in the production of the graft polymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (end group A) manufactured by TOAGOSEI CO., LTD. can be used. Acryl fluorenyl polymethyl methacrylate), AS-6 (polystyrene based terminal group is methacryl fluorenyl), AN-6S (styrene and acrylonitrile whose terminal group is methacryl fluorenyl) Copolymer), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACEL FM5 manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD. (ε-caprolactone of 2-hydroxyethyl methacrylate) 5 molar equivalents of the finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 mil equivalents of the finished product), and the polyester-based macromonomer described in JP-A No. 2-272009.

As the block type polymer, a block type polymer described in, for example, JP-A-2003-49110, and JP-A-2009-52010 is preferable.

The resin used as the dispersing agent preferably contains a repeating unit having an acid group. When the resin contains a repeating unit having an acid group, when a colored pattern is formed by photolithography, the residue generated on the base of the colored pixel can be further reduced.

The repeating unit having an acid group can be constituted using a monomer having an acid group. Examples of the acid group-derived monomer include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.

Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid. Dimer and the like. Further, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride or cyclohexane dicarboxylic anhydride may be used. The reactant is ω-carboxy-polycaprolactone mono(meth)acrylate or the like. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride can be used. Among them, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a monomer such as maleic anhydride, phthalic anhydride, succinic anhydride, or cyclohexane, from the viewpoint of development removability of the unexposed portion. An addition reactant of a cyclic anhydride such as an alkanedicarboxylic acid anhydride is preferred.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid and the like.

Examples of the vinyl monomer having a phosphoric acid group include mono(2-propenyloxyethyl ester) phosphate and mono(1-methyl-2-propenyloxyethyl phosphate).

Further, as a repeating unit having an acid group, the description of paragraphs 0067 to 0069 of JP-A-2008-165059 can be referred to, and the content is included in the present specification.

Further, in the present invention, as the dispersing agent, a graft copolymer comprising a repeating unit represented by any one of the formula (A1) and the formula (A2) and a repeating unit having an acid group can be used. The graft copolymer can be used as an acidic dispersant.

[Chemical Formula 22]

In the general formulae (A1) and (A2), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent -CO-, -C(=O)O-. , -CONH-, -OC(=O)- or phenylene, and L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently represent a monovalent organic group. The bases, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferred. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

As R ¹ , R ² , R ⁴ and R ⁵ , a hydrogen atom is preferred, and as R ³ and R ⁶ , a hydrogen atom or a methyl group is also preferable from the viewpoint of the adsorption efficiency on the surface of the pigment.

X ¹ and X ² each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)- or a phenylene group. Among them, from the viewpoint of the sorption property to the pigment, -C(=O)O-, -CONH-, and phenylene are preferred, and -C(=O)O- is preferred.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. As the divalent organic linking group, a substituted or unsubstituted alkylene group, a divalent organic linking group composed of an alkylene group and a hetero atom or an alkylene group and a partial structure containing a hetero atom are preferred.

The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

Examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, an oxygen atom or a nitrogen atom is preferred.

As the divalent organic linking group, from the viewpoint of the sorption property to the pigment, it is preferred to have a terminal group selected from -C(=O)-, -OC(=O)- at the terminal of the above alkylene group. a hetero atom of -NHC(=O)- or a partial structure containing a hetero atom, which is bonded to an adjacent oxygen atom via a hetero atom or a partial structure containing a hetero atom. Here, the adjacent oxygen atom means the general formula (A1) in the L ^1, and the formula (A2), the L ^2, an oxygen atom of the side chain end side key junction.

A ¹ and A ² each independently represent a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferred. The substituents described in Paragraph No. 0027 of JP-A-2009-256572 are incorporated herein by reference.

A ¹ and A ^{2 are} a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 carbon atoms from the viewpoint of dispersion stability and developability. The cyclic alkyl group of -20 is preferable, the linear alkyl group having 4 to 15 carbon atoms, the branched alkyl group having 4 to 15 carbon atoms, and the cyclic alkyl group having 6 to 10 carbon atoms are More preferably, a linear alkyl group having 6 to 10 carbon atoms or a branched alkyl group having 6 to 12 carbon atoms is further more preferable.

m and n each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferred, and 5 is most preferred.

p and q each independently represent an integer of 1 to 100. It is also possible to mix two or more different types of p and different ones of q. From the viewpoint of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, still more preferably from 5 to 20.

For the details of the repeating unit represented by the formula (A1) and the repeating unit represented by the formula (A2), the contents of the paragraphs 0060 to 0084 of JP-A-2012-173356 can be referred to. Incorporated into this specification.

Examples of the repeating unit having an acid group include the above.

The details of the graft copolymer described above can be referred to in the specification of the paragraphs 0060 to 0109 of JP-A-2012-173356. Specific examples of the graft copolymer include the following.

[Chemical Formula 23]

Further, in the present invention, an oligomeric imine (Oligoimine) resin containing a nitrogen atom in at least one of a main chain and a side chain can be used as the dispersant. The oligomeric imide resin is preferably a resin having a repeating unit and a side chain and having a basic nitrogen atom in at least one of a main chain and a side chain, wherein the repeating unit has _a functional group having a pKa 14 or less Part of the structure X, the side chain contains an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.

Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligomeric imide resin preferably has a structure having a nitrogen atom having a salt strength of pK _b 14 or less, and more preferably has a structure having a nitrogen atom of pK _b 10 or less.

In the present invention, the salt refers to the strength pK _b pK _b at temperature 25 ℃, based index for quantitatively showing one salt intensity, the basicity constant based same meaning. The salt strength pK _b and the acid strength pK _a described later have _a relationship of pK _b =14-pK _a .

The oligomeric imine resin is preferably a repeating unit (i) and a side chain (ii), wherein the repeating unit (i) is selected from the group consisting of poly(lower alkylene imine) repeating units, polyallyl Repeating of at least one of a basic amine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit having a basic nitrogen atom And a partial structure X having a functional group bonded to a basic nitrogen atom and containing pK _a 14 or less, the side chain (ii) having an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.

The poly(lower alkylene imide) may be in the form of a chain or a mesh. Here, in the present invention, the lower alkyleneimine means an alkyleneimine having an alkylene chain having 1 to 5 carbon atoms.

It is preferred that the repeating unit (i) forms a main chain portion in the oligomeric imide resin. The number average molecular weight of the main chain portion, that is, the number average molecular weight of the side chain (ii) portion removed from the oligomeric imide resin is preferably from 100 to 10,000, more preferably from 200 to 5,000, and further preferably from 300 to 2,000. optimal. The number average molecular weight of the main chain portion can be determined from the ratio of the hydrogen atom integrated value of the terminal group and the main chain portion measured by the nuclear magnetic resonance spectroscopy, or the oligomer or polymer containing the amine group as a raw material can be determined. The molecular weight of the main chain portion was determined by the molecular weight.

One of the most preferable examples of the oligo-imine-based resin is a state in which a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) are contained.

[Chemical Formula 24]

In the general formulae (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5, and * represents a repeating unit. In the connection portion, X represents a group having _a functional group of pK _a 14 or less, and Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

The oligomeric imide resin further preferably contains a repeating unit represented by the formula (I-3). According to this state, the dispersibility of the coloring agent or the like is further improved.

[Chemical Formula 25]

In the formula (I-3), R ¹ , R ² and a have the same meanings as R ¹ , R ² and a in the formula (I-1). Y' represents an oligomer chain or a polymer chain having an anion group having an atomic number of 40 to 10,000. The compound (I-3) can be formed by adding an oligomer or a polymer having a group which forms a salt by reacting with an amine in a resin having a primary or secondary amine group in the main chain portion. The repeating unit indicated in .

In the general formula (I-1), the general formula (I-2) and the general formula (I-3), R ¹ and R ² are preferably a hydrogen atom. From the viewpoint of raw material availability, a is preferably 2.

The oligomeric imide resin may contain a lower group having a primary or tertiary amine group in addition to the repeating unit represented by the formula (I-1), the formula (I-2) and the formula (I-3). The alkylimine is used as a repeating unit. Further, the nitrogen atom in the lower alkylene imine repeating unit may be further bonded to a group represented by X, Y or Y'.

The repeating unit represented by the formula (I-1) is preferably contained in an amount of from 1 to 80 mol%, more preferably from 3 to 50 mol%, based on the total repeating unit contained in the oligomeric imide resin.

The repeating unit represented by the formula (I-2) is preferably 10 to 90 mol%, and preferably 30 to 70 mol%, based on the total repeating unit contained in the oligomeric imide resin.

From the viewpoint of dispersion stability and hydrophilic-hydrophobic balance, the content ratio of the repeating unit (I-1) and the repeating unit (I-2) [(I-1): (I-2)] is expressed in terms of molar ratio. The range of 10:1 to 1:100 is preferable, and the range of 1:1 to 1:10 is more preferable.

Further, the repeating unit represented by the formula (I-3) used in combination as needed contains an oligomer chain having an atomic number of 40 to 10,000 or a partial structure of the polymer chain Y' and a nitrogen atom ionic bond of the main chain. In the total repeating unit contained in the oligoenimine resin, it is preferably from 0.5 to 20 mol%, and preferably from 1 to 10 mol%, from the viewpoint of the effect. Further, it was confirmed by ion spectrometry or salt titration that the polymer chain Y' was ion-bonded.

The oligo-imine-based resin may be a compound described in paragraphs 0021 to 0018 of JP-A-2009-258668 and paragraphs 0021 to 0080 of JP-A-2009-203462. This is incorporated into the present specification.

Further, in the present invention, as the acidic dispersing agent, a resin having an acid group and an unsaturated double bond described in paragraphs 0020 to 0075 of JP-A-2008-165059 can be used.

A dispersant can be obtained as a commercial product. As a specific example, "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; "DISPERBYK-101 (polyamide-amine phosphoric acid) manufactured by BYK-Chemie GmbH Salt), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamine), 161, 162, 163, 164, 165, 166, 170, 171 , 174, 176, 180, 182, 2000, 2001, 2050, 2150, P104, P105, LPN21116"; "BYK-6919" manufactured by BYK-Chemie GmbH, "EFKA 4047, 4050-4010 ~ 4165" manufactured by EFKA Corporation Amino acid ester), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid) Polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative); "AJISPER PB821, PB822, PB880, PB881" manufactured by AJINOMOTO FINE-TECHNO Co., Inc.; manufactured by KYOEISHA Chemical Co., Ltd. "FLOWLEN TG-710 (polyurethane oligomer)", "POLYFLOW No. 50E, No. 300 (propylene Acid Copolymer)"; DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA- manufactured by KUSUMOTO Chemicals, Ltd. 705, DA-725"; "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate)", "HOMOGENOL L-18" manufactured by KAO Corporation (Polymer polycarboxylic acid)", "EMULGEN920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN86 (stearylamine acetate)"; "SOLSPERSE5000" manufactured by LUBRIZOL JAPAN, LTD. (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the terminal portion), 24000, 28000, 32000, 38500 (graft type polymer)"; "NIKKOR T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko Chemicals Co., Ltd.; HINOACT T-8000E manufactured by KAWAKEN FINE CHEMICALS CO., LTD.; organic 矽 manufactured by SHIN-ETSU CHEMICAL CO., LTD. Alkyl polymer KP341; "W001: cationic surfactant" manufactured by YUSHO CO., LTD., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octane Nonionic surfactants such as phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, "W004, Anionic surfactant such as W005, W017", "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 manufactured by MORISHITA & CO., LTD. Polymer dispersant such as "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" manufactured by SUN NOPCO LIMITED, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68 manufactured by ADEKA CORPORATION" ", L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "IONET (trade name) S-20" manufactured by SANYO CHEMICAL INDUSTRIES, LTD. Also, ACRYBASE FFS-6752, ACRYBASE FFS-187, ACRYCURE-RD-F8, and CYCLOMER P can be used.

Further, the resin described by the above dispersant may be used in applications other than the dispersant. For example, it can also be used as a binder.

<<<Alkali Soluble Resin>>

The colored curable composition of the present invention can contain an alkali-soluble resin as a resin. The developability and pattern formability are improved by containing an alkali-soluble resin. In addition, alkali-soluble resins can also be used as a dispersant and a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably from 5,000 to 100,000. Further, a number average molecular weight (Mn) of from 1,000 to 20,000 is preferred.

The alkali-soluble resin may be a linear organic high molecular polymer, or may have at least one base which promotes alkali solubility in a molecule (a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkaloid-soluble resin is appropriately selected.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of controlling developability, an acrylic resin, an acrylamide resin, and an acrylic/acrylamide copolymer resin are preferable.

Examples of the group which promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are soluble in an organic solvent, and can be developed by using a weak alkali aqueous solution. It is preferred, and (meth)acrylic acid is preferred as a preferred one. These acid groups may be used alone or in combination of two or more.

In the case of producing an alkali-soluble resin, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally set.

As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolak type resin; and an acid cellulose derivative having a carboxyl group in a side chain; and an acid anhydride added to a polymer having a hydroxyl group; Adult. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., and examples of the vinyl compound include styrene, α-methylstyrene, and vinyltoluene. , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, methacrylic tetrahydrofurfuryl ester, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. Examples of the N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide. Further, the other monomers copolymerizable with the (meth)acrylic acid may be used alone or in combination of two or more.

Further, in order to improve the crosslinking efficiency of the color hardening composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryl fluorenyl group. An alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain.

The alkali-soluble resin containing a polymerizable group is preferably a resin or the like which is obtained by reacting an isocyanate group with a hydroxyl group to leave an unreacted isocyanate group, and a polymerizable group such as a (meth)acryl fluorenyl group. An alkali-soluble resin obtained by reacting with a carboxyl group-containing acrylic resin; and modified by a urethane; a resin having a carboxyl group and a compound having an epoxy group and a polymerizable double bond in the molecule; An alkali-soluble resin obtained by the reaction; an acid pendant acrylic acrylate resin; an alkali-soluble resin obtained by reacting a hydroxyl group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; An alkali-soluble resin obtained by reacting an acrylic resin with a compound having an isocyanate and a polymerizable group; and the following resin is subjected to alkaline treatment as described in JP-A-2002-229207 and JP-A-2003-335814 The alkali-soluble resin obtained has a halogen atom or a sulfonic acid group at the α-position or the β-position in the side chain. Group of the ester group.

Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON SHARES CO., LTD.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), and VISCOAT R. -264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), and Ebecryl 3800 (DAICEL UCB CO.) , manufactured by LTD., Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), and the like.

As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl copolymer may be preferably used. And a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, it is also possible to use 2-hydroxyethyl (meth) acrylate copolymerized, and 2-hydroxypropyl (meth)acrylate/polyphenyl group described in JP-A-7-140654 Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like.

It is also preferred that the alkali-soluble resin comprises a polymer (a) which will contain a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (below) Further, the monomer components of these compounds are sometimes referred to as "ether dimers".

[Chemical Formula 26]

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[Chemical Formula 27]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP-A-2010-168539 can be referred to.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. a linear or branched alkyl group such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; An alkyl group substituted with an alkoxy group such as an oxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among them, in particular, from the viewpoint of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is not easily desorbed from a primary or secondary carbon by acid or heat is preferred.

Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate and diethyl-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butyl)-2,2'-[oxy double (methylene Base]] bis-2-acrylate, bis(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(stearyl)-2,2' -[oxybis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2- Ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis (methylene Bis-2-]acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butylcyclohexyl)-2,2'-[oxybis(methylene) )] bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tricyclodecyl)- 2,2'-[oxybis(methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate , diamantyl-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxy Bis(methylene)] bis-2-acrylate. Wherein, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2 - acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene)] double -2-Acrylate is especially preferred. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the general formula (ED) may also copolymerize other monomers.

The alkali-soluble resin may also contain a structural unit derived from a compound represented by the following formula (X).

[Chemical Formula 28]

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or may have a benzene ring having 1 to 20 carbon atoms. alkyl. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ has preferably 2 to 3 carbon atoms. Further, the alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R ₃ may contain a benzene ring. The alkyl group containing a benzene ring represented by R ₃ may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.

The alkali-soluble resin can be incorporated into the description after the following paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to [0685] to [0700] of the specification of the Japanese Patent Application Publication No. 2012/0235099) In the specification of the present application.

In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in JP-A-2012-32767, the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesive resin used in the examples, The adhesive resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, paragraphs 0092 to 0098 of JP-A-2011-242752, and the examples are used. The adhesive resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application.

The acid value of the alkali-soluble resin is preferably from 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and still more preferably 120 mgKOH/g or less.

When the coloring curable composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably from 1 to 15% by mass based on the total solid content of the colored curable composition, and more preferably from 2 to 12% by mass. ～10% by mass is further preferred. The colored curable composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. In the case where two or more kinds of alkali-soluble resins are contained, the total amount thereof is preferably in the above range.

<<Pigment Derivative>>

The colored curable composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted by an acidic group, a basic group or a phthalyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility and dispersion stability of the colorant A. A pigment derivative having a basic group is particularly preferred. Further, in the combination of the above resin (dispersant) and the pigment derivative, it is preferred that the dispersant is an acidic dispersant and the pigment derivative has a combination of basic groups.

Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. A purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a Shilin pigment, a metal complex pigment, and the like.

Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferred, a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred.

In the case where the colored curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30% by mass based on the mass of the colorant A, and more preferably from 3 to 20% by mass. The pigment derivative may be used alone or in combination of two or more.

<<Photopolymerization initiator>>

The color hardening composition of the present invention may further contain a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-stimulated sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone.

Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, and a phosphine oxide compound. , metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron mismatch A compound of the group consisting of a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound is preferred.

a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are Further preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when the colored curable composition of the present invention is used in the production of a color filter of a solid-state image sensor, it is necessary to form a fine pattern in a tapered shape, so that curing is performed and development is performed without residue on the unexposed portion. More important. From such a viewpoint, it is especially preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, exposure by a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator. In view of this point, it is preferable to use a ruthenium compound as a photopolymerization initiator when forming a fine pattern like a solid-state image sensor. Moreover, the transferability can be more optimized by using a ruthenium compound.

Specific examples of the photopolymerization initiator can be referred to the specification of the present application by referring to paragraphs 0265 to 0268 of JP-A-2013-29760, for example.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Patent No. 4,258,899 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF SE) can be used.

As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF SE) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm.

As the mercaptophosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF SE) can be used.

As the photopolymerization initiator, a ruthenium compound is more preferable.

As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.

Examples of the ruthenium compound which can be suitably used in the present invention include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3- Propyl methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one and 2-ethoxycarbonyloxy Amino-1-phenylpropan-1-one and the like.

Further, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also mentioned. The compound described in each of the publications such as JP-A-2000-80068, JP-A-2000-80068, and JP-A-2006-342166, and the like.

IRGACURE-OXE01 (manufactured by BASF SE) and IRGACURE-OXE02 (manufactured by BASF SE) can also be suitably used in the commercial product. Further, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used.

In addition, as the ruthenium compound other than the above-mentioned, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of the carbazole, and a U.S. Patent No. 7,626,957 in which a hetero substituent is introduced at the benzophenone site can be used. The compound described in the Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone oxime compound described in Japanese Laid-Open Patent Publication No. 2009-131189. The compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption of 405 nm, and has a good sensitivity to a g-line light source, as described in JP-A-2009-221114. Compounds, etc.

For example, it is preferable to refer to paragraphs 0274 to 0275 of JP-A-2013-29760, which is incorporated herein by reference.

Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be an oxime compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 29]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred.

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent.

The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

Specific examples of the compound represented by the formula (OX-1) are shown below, but the present invention is not limited to these.

[Chemical Formula 30]

The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and preferably having a higher absorbance at 365 nm and 455 nm.

Among the ruthenium compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, still more preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be preferably measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

The photopolymerization initiator to be used in the present invention may be used in combination of two or more kinds as needed.

In the case where the colored curing composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, based on the total solid content of the colored curable composition, and is from 0.5 to 30% by weight. The mass % is more preferably 1 to 20% by mass. Within this range, more excellent sensitivity and pattern formation can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. In the case where two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<<Polymerization inhibitor>>

In the color hardening composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored curable composition, it is preferred to add a small amount of a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-sulfur. Di-bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first Salt and so on.

In the case where the colored curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from about 0.01 to 5% by mass based on the mass of the colored curable composition.

The colored curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

<<Interfacial active agent>>

From the viewpoint of further improving the coatability, various surfactants may be added to the colored curable composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

For example, when a coating liquid is prepared by containing a fluorine-based surfactant, liquid characteristics (especially fluidity) at the time of preparation of a coating liquid are further improved. In other words, when a film is formed using a color-curable composition containing a fluorine-based surfactant, the interface tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is moistened. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to further appropriately form a film having a small thickness unevenness and a uniform thickness.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, still more preferably from 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in thickness uniformity and liquid-saving property of the coating film, and the solubility in the colored curable composition is also good.

Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, and MEGAFAC F479. , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781 (above, manufactured by DIC Corporation); FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above, manufactured by SUMITOMO 3M Limited); SURFLON S-382, SURFLON SC-101, SURFLON SC- 103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.); PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like.

As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, propoxylated glycerol, ethoxylated). Glycerin, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Laurate, polyethylene glycol distearate, sorbitan fatty acid ester (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, manufactured by BASF SE, 904, 150R1), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), and the like. Further, PIONIN D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD. can also be used.

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), and an organic siloxane polymer KP341 (SHIN-ETSU CHEMICAL CO.). (manufactured by LTD.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (manufactured by YUSHOCO., LTD.), etc. .

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHOCO., LTD.).

Examples of the anthrone-based surfactants include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", and "TORAY SILICONE" manufactured by DOW CORNING TORAY CO., LTD. SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", "TORAY SILICONE SH8400"; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by MOMENTIVE PERFORMANCE MATERIALS Inc. ""TSF-4452"; "KP341", "KF6001", "KF6002" manufactured by SHIN-ETSU CHEMICAL CO., LTD.; "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie CO., LTD. "Wait.

In the case where the colored curable composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass based on the total mass of the colored curable composition, and more preferably 0.005 to 1.0% by mass. .

The colored curable composition of the present invention may contain only one type of surfactant, or may contain two or more types. In the case where two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.

<<decane coupling agent>>

The color hardening composition of the present invention may contain a decane coupling agent.

As the decane coupling agent, a decane compound having at least two functional groups having different reactivity in one molecule is also preferable, and those having an amine group and an alkoxy group as a functional group are particularly preferable. As such a decane coupling agent, for example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602) is available. N-β-Aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) , N-β-aminoethyl-γ-aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyl-trimethoxy Base decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyl-triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBE- 903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBM-503), and the like. The details of the decane coupling agent can be referred to in the present specification by referring to the descriptions of paragraphs 0155 to 0158 of JP-A-2013-254047.

In the case where the colored curable composition of the present invention contains a decane coupling agent, the content of the decane coupling agent is preferably 0.001 to 20% by mass based on the total solid content of the colored curable composition, and more preferably 0.01 to 10% by mass. Preferably, 0.1% by mass to 5% by mass is particularly preferred.

The colored curable composition of the present invention may contain only one type of decane coupling agent, or may contain two or more types. In the case where two or more kinds of decane coupling agents are contained, the total amount thereof is preferably in the above range.

<<Other additives>>

In the color hardening composition of the present invention, various additives such as a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like can be blended as needed. The above-mentioned additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, and the contents are incorporated in the specification of the present application.

In the coloring-curable composition of the present invention, the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the above-mentioned publication can be contained.

<Method for Preparing Colored Curable Composition>

The color hardening composition of the present invention is prepared by mixing the above components.

In the preparation of the colored curable composition, the components constituting the colored curable composition may be uniformly blended, or may be blended one by one after the components are dissolved and dispersed in a solvent. Moreover, the order of placement and the working conditions at the time of fitting are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a colored curable composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and when used (at the time of coating) These were mixed to prepare a composition.

The colored hardenable composition of the present invention is preferably filtered by a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without particular limitation as long as it is used for filtration purposes or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and super) may be mentioned. A filter composed of a high molecular weight or the like. Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The filter has a pore diameter of about 0.01 to 7.0 μm, preferably 0.01 to 3.0 μm, and more preferably 0.05 to 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which hinders uniform and smooth preparation of the colored curable composition in the subsequent step.

When using a filter, it is also possible to combine different filters for use. In this case, the first filter may be used for filtration only once or twice or more.

Further, the first filter having different pore diameters may be combined within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS K.K. (Mykrolis Corporation), or KITZ MICROFILTER CORPORATION.

The second filter can be formed of the same material or the like as the first filter described above.

For example, the filtration by the first filter may be performed only by the dispersion, or the second filtration may be performed after mixing the other components.

Since the colored curable composition of the present invention can form a cured film excellent in light resistance, transfer property, and flatness, it can be suitably used for forming a coloring layer of a color filter. Further, the colored curable composition of the present invention can be suitably used for forming a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), and a color filter used in an image display device such as a liquid crystal display device. The use of colored patterns such as light sheets. In addition, it is also suitable for use in printing inks, inkjet inks, and coatings. Among them, it is suitable for use in the manufacture of color filters for solid-state imaging devices such as CCDs and CMOSs.

<Color filter, pattern forming method, and method of manufacturing color filter>

Next, the pattern forming method will be described in detail by the manufacturing method. The color filter is described in detail by its manufacturing method. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will be described.

The color filter of the present invention is obtained by using the colored curable composition of the present invention.

In the pattern forming method of the present invention, the colored curable composition layer of the present invention is used to form a colored curable composition layer on a support, and an unnecessary portion is removed to form a colored pattern.

The pattern forming method of the present invention can be suitably applied to a colored pattern forming a color filter.

The pattern forming method of the present invention may be patterned by a so-called photolithography method or may be patterned by a dry etching method.

That is, the first aspect of the method for producing a color filter of the present invention includes the step of forming a colored curable composition layer on a support by using the colored curable composition of the present invention; and the colored curable composition layer a step of exposing to a pattern; and a step of developing and removing the unexposed portion to form a colored pattern. If necessary, a step of baking the colored curable composition layer (prebaking step) and a step of baking the developed colored pattern (post-baking step) may be also provided.

Further, the second aspect of the method for producing a color filter of the present invention includes the step of forming a colored curable composition layer on a support by using the colored curable composition of the present invention, and curing to form a colored layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask to dry-etch the colored layer to form The step of coloring the pattern.

The color filter of the present invention can be suitably obtained by the above production method. Hereinafter, the details will be described.

<<Steps of forming a color hardening composition layer>>

In the step of forming the colored curable composition layer, the colored curable composition layer is formed on the support using the colored curable composition of the present invention.

As the support, for example, a substrate for a solid-state imaging device in which a solid-state imaging device (light-receiving element) such as a CCD or a CMOS is provided on a substrate (for example, a germanium substrate) can be used.

The colored pattern in the present invention may be formed on the solid-state imaging device forming surface side (surface) of the solid-state imaging device substrate, or may be formed on the solid-state imaging device non-forming surface side (back surface).

If necessary, in order to improve the adhesion to the upper layer, prevent the scattering of the substance, or achieve flattening of the surface of the substrate, an undercoat layer may be provided on the support.

As a method of applying the color hardening composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The drying (prebaking) of the colored hardening composition layer applied to the support can be carried out at a temperature of 50 to 140 ° C for 10 to 300 seconds using a hot plate, an oven or the like.

<<Exposure step>>

Next, the colored curable composition layer formed on the support is exposed in a pattern (exposure step). For example, the coloring-curable composition layer formed on the support can be exposed by exposure using a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. Thereby, the exposed portion can be hardened.

As the radiation (light) which can be used for exposure, it is preferable to use ultraviolet rays such as g-line or i-line (i-line is preferable). The irradiation amount (exposure amount) is preferably, for example, 30 to 1,500 mJ/cm ² , more preferably 50 to 1000 mJ/cm ^{2 , and most} preferably 80 to 500 mJ/cm ² .

The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and still more preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, it is easy to obtain high resolution and high adhesion.

<<Pattern forming step>>

Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development removal of the unexposed portion can be performed using a developer. Thereby, the colored curable composition layer of the unexposed portion in the exposure step is dissolved in the developer, and only the portion where the light is hardened remains.

An organic alkaline developing solution in which the developer does not damage the solid image sensor, the circuit, or the like of the substrate is preferable.

The temperature of the developer is preferably, for example, 20 to 30 °C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the developer may be oscillated every 60 seconds, and the step of re-supplying the developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydroxide. An organic basic compound such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5.4.0]-7-undecene. The alkaline aqueous solution obtained by diluting the alkali chemicals with pure water as a developing solution is preferably used in an amount of 0.001 to 10% by mass (preferably 0.01 to 1% by mass).

Further, an inorganic base can also be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable.

Further, in the case of using a developer composed of such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

After the development, it is preferred to carry out heat treatment (post-baking) after drying. When a multicolor coloring pattern is formed, it is possible to repeat the steps for each color to produce a cured film. Thereby, a color filter can be obtained.

The post-baking is used for heat treatment after development in which the curing is made safe, and the heating temperature is preferably 100 to 240 ° C, more preferably 200 to 240 ° C.

The film after development can be post-baked in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high frequency heater.

The color filter of the present invention can be suitably applied to a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for use in a high-resolution CCD, CMOS, or the like of more than one million pixels.

The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

The coloring pattern (colored pixel) of the color filter of the present invention has a film thickness of preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

In the case of forming a pattern by dry etching, the contents of this application can be incorporated by reference to the contents of the Japanese Patent Application Publication No. 2013-64993.

<Solid image sensor>

The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The solid-state imaging device has a plurality of photodiodes in a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) on a support, and a transfer electrode composed of polyfluorene or the like. The photodiode and the transfer electrode have a light-shielding film made of tungsten or the like that opens only the light-receiving portion of the photodiode, and the light-shielding film is formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. A device protective film made of tantalum nitride or the like has a color filter for a solid-state imaging device of the present invention on a device protective film.

Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and on the lower side of the color filter (the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

<Image display device>

The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is especially suitable for the use of liquid crystal display devices. The liquid crystal display device including the color filter of the present invention can display a high-quality image in which the hue of the displayed image is good and the display characteristics are excellent.

The definition of the display device and the details of each display device are described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibuki Shun, "Sangyo Tosho" Co., Ltd., issued in the first year of Heisei)" and so on. Further, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a color TFT (Thin Film Transistor) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field pulsation method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment) is expanded, or STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend).

Moreover, the color filter of the present invention can also be provided in a bright and high-resolution COA (Color-filter On Array) method. In the liquid crystal display device of the COA type, in addition to the usual required characteristics as described above, in addition to the usual required characteristics, the required characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance may be required. . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described, for example, in "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center, Inc. Research and Research Department, issued in 2001)", page 43 and the like.

In the liquid crystal display device including the color filter of the present invention, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle assurance film, and the like are used. It is composed of various components. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in "The Market of Materials and Chemical Products for Liquid Crystal Display (Island Kent Co., Ltd., CMC Co., Ltd., 1994)", "The Status and Future of the 2003 Liquid Crystal Related Markets (Vol. 2)" "FUJI CHIMERA RESEARCH INSTITUTE, INC., issued in 2003)".

The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al), monthly publication December 2005, pages 18 to 24 (Island Kangyu), monthly publication 25 to 30 pages (Yamamu Takamori), and the like.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and by using red, green, and blue light-emitting diodes As a backlight, a body (LED) light source can provide a liquid crystal display device having high brightness and high color reproducibility.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are mass standards.

<Measurement of Weight Average Molecular Weight and Number Average Molecular Weight>

The weight average molecular weight and the number average molecular weight were determined by the following methods. Column type: TSKgelSuperAW4000, TSKgelSuperAW3000, TSKgelSuperAW2500 and TSKgelSuperAW2500 were connected to develop solvent: N-methylpyrrolidone (10mmol/L containing LiBr) Column temperature: 50°C Flow rate (sample injection amount): 20μL Flow rate: 0.25ml/ Min Device name: HLS-8220 GPC calibration curve manufactured by TOSOH Corporation Base resin: Polystyrene

<Method for measuring acid value>

The measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the obtained solution was obtained by using a potentiometric titration apparatus (trade name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). Neutralization titration was carried out in a 0.1 mol/L aqueous sodium hydroxide solution at 25 °C. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated from the following formula.

A=56.11×Vs×0.1×f/w A: Acid value (mgKOH/g) Vs: The amount of 0.1 mol/L sodium hydroxide aqueous solution required for titration (mL) f: 0.1 mol/L sodium hydroxide aqueous solution Titration (Titer) w: Determination of sample mass (g) (solid content conversion)

<Method for measuring amine value>

The measurement sample was dissolved in acetic acid, and the obtained solution was subjected to a 0.1 mol/L perchloric acid/acetic acid solution using a potentiometric titration apparatus (trade name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). And titration. The inflection point of the titration pH curve was taken as the end point of the titration and the amine value was calculated from the following formula.

B = 56.11 × Vs × 0.1 × f / w B: Amine value (mgKOH / g) Vs: 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL) f: 0.1 mol / L perchlorine The titer of the acid/acetic acid solution w: the mass (g) of the measured sample (solid content conversion)

(synthesis example)

[Chemical Formula 31]

<Synthesis Example of Colorant A-1>

50 parts of DCSF (manufactured by Chugai Kasei Company, Limited), 74.76 parts of 2,6-dimethylaniline, 27.58 parts of zinc chloride, and 200 parts of cyclobutyl hydrazine were placed in a flask, and stirred at an external temperature of 200 ° C for 4 hours. . Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 500 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. The crystals were dispersed and washed with 300 parts of 40-degree acetonitrile, collected by filtration, and dried by air drying for 10 hours to obtain 46.5 parts (yield: 65.6%) of the coloring agent A-1.

<Synthesis of Intermediate 1>

20 parts of the colorant A-1 and 106 parts of phosphorus oxychloride were placed in a flask, and stirred at 60 ° C for 2 hours. The obtained reaction solution was allowed to cool to room temperature, and the reaction solution was dropped into 1500 parts of ice water and stirred for 30 minutes. The obtained crystal was filtered, washed with 200 parts of water, and dried by air drying for 10 hours to obtain 18.5 parts (yield: 89.4%) of Intermediate 1.

<Synthesis of Colorant A-4>

7 parts of intermediate 1, 2.05 parts of benzenesulfonamide were dissolved in 40 parts of chloroform, and diazabicyclo (1,8-dioxabicyclo[5.4.0]undec-7-ene) was added dropwise (1, 8-diazabicyclo [5.4.0]undec-7-ene) 2.32 parts, stirred at room temperature for 1 hour. Then, 100 parts of water was placed in the obtained reaction solution for washing with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, and purified by column chromatography, and concentrated under reduced pressure to give 3 (yield: 34%) of coloring agent A-4.

<Synthesis Example of Colorant A-2>

The coloring agent A-2 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,6-diethylaniline.

<Synthesis Example of Colorant A-3>

The coloring agent A-3 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,6-diisopropylaniline.

<Synthesis Example of Colorant A-5>

The coloring agent A-5 was synthesized by changing the benzenesulfonamide used in the synthesis of the colorant A-4 to trifluoromethylsulfonamide.

<Synthesis Example of Colorant A-6>

The coloring agent A-6 was synthesized by changing the benzenesulfonamide used in the synthesis of the colorant A-4 to toluenesulfonamide.

<Synthesis Example of Colorant A-7>

The coloring agent A-7 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,4,6-trimethylaniline.

<Synthesis Example of Colorant A-8>

[Chemical Formula 32]

50 parts of DCSF (manufactured by CHUGAI KASEI CO., LTD.), 52.5 parts of 2,6-diisopropylaniline, and 200 parts of cyclobutyl hydrazine were placed in a flask, and stirred at an external temperature of 80 °C for 4 hours. Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 500 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. After the crystals were subjected to dispersion washing with 300 parts of acetonitrile of 40 degrees, the mixture was collected by filtration and dried by air drying for 10 hours to obtain 28 parts (yield: 45%) of Intermediate 2.

25 parts of the intermediate 2, 14.4 parts of 2,6-dimethylaniline, 11.1 parts of zinc chloride, 100 parts of cyclobutyl hydrazine were added, and stirred at an external temperature of 200 °C for 4 hours. Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 200 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. After dispersing and washing the crystals with 120 parts of acetonitrile at 40 degrees, the mixture was collected by filtration and dried by air drying for 10 hours to obtain 25.1 parts (yield: 86%) of the coloring agent A-8.

<Synthesis Example of Colorant A-9>

The 2,6-dimethylaniline used in the synthesis of the colorant A-1 was changed to N-(3-amino-2,4,6-trimethylphenyl)acetamide to synthesize a color former. A-9.

<Synthesis Example of Colorant A-10>

The coloring agent A-10 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2-methylaniline.

[Chemical Formula 33]

<Evaluation of Solvent Solubility of Colorant>

To the sample vial, 0.1 g of the coloring agent was placed, and then 10 ml of the organic solvent shown in the following Table 1 was placed in a Whole Pipette, and the mixture was treated with ultrasonic waves for 3 minutes after the stopper. The obtained solution was allowed to stand in a water bath at 23 ° C for 60 minutes. 5 ml of this supernatant was filtered with a membrane filter made of PTFE having a pore size of 5 μm, and further, a membrane filter made of PTFE having a pore diameter of 0.25 μm was used for filtration to remove insoluble matter.

The absorbance spectroscopy of the filtrate was measured using an ultraviolet-visible spectrophotometer (CARY 5000 manufactured by AGILENT Corporation) and using a cell of 1 cm. The absorbance at the maximum absorption wavelength of each colorant was determined. At this time, when the absorbance at the maximum absorption wavelength is less than 2, it can be evaluated that the colorant is substantially not dissolved in the organic solvent, and the solubility of the colorant can be evaluated to be 1 (g/100 g of the organic solvent) or less. Further, the measurement limit of the absorbance measured by the present measurement method was 0.005. The results are shown in Table 1. PGMEA in the table is an abbreviation for propylene glycol monomethyl ether acetate.

[Table 1]

As shown in the above table, the color formers of A-1 to A-10 are substantially insoluble in PGMEA, cyclohexanone, and cyclopentanone, and the solubility in these organic solvents is 1 (g/100 g of organic solvent) or less.

<Preparation of dispersion using (A) colorant>

The (A) colorant, (B) dispersant, (C) pigment derivative, (H) dye, and solvent were mixed at a ratio shown in the following Table 2, and after stirring and mixing uniformly, a diameter of 0.5 mm was used. The zirconium beads were dispersed by a bead mill for 5 hours to prepare a dispersion.

[Table 2]

The compounds described in the table are as follows.

(A) Colorant A-1 to A-10: Color former A-1 to A-10 R-1 to R-5 of the above structure: comparative compound (structure described below)

[Chemical Formula 34]

(B) Dispersant

[table 3]

[Chemical Formula 35]

(C) Pigment Derivative C-1: The following structure

[Chemical Formula 36]

(H) Dye H-1 to H-3: the following structure

[Chemical Formula 37]

1. Preparation of colored curable composition

1-1. Preparation of pigment dispersion

<Preparation of Blue Pigment Dispersion P1>

The blue pigment dispersion P1 was prepared as follows.

A mixture of 13.0 parts of CIPigment Blue 15:6 (blue pigment; hereinafter also referred to as "PB15:6") (blue pigment, average particle diameter 55 nm), 5.0 parts of Disperbyk 111 as a dispersing agent, and 82.0 parts of PGMEA was mixed. It was mixed and dispersed by a bead mill (zirconium beads 0.3 mm diameter) for 3 hours. Then, a high-pressure disperser NANO-3000-10 (manufactured by NIHON BEE CO., LTD.) equipped with a pressure-reducing mechanism was further used, and the mixture was dispersed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . deal with. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid P1 (CIPigment Blue 15:6 dispersion liquid, pigment concentration 13%) used in the color hardening composition of the examples or the comparative examples.

When the average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), the obtained blue pigment dispersion liquid P1 was 24 nm.

<Preparation of Blue Pigment Dispersion P2>

19.4 parts by mass of PB15:6 (average particle diameter: 55 nm), 2.95 parts by mass of BYK-161 (manufactured by BYK-Chemie GmbH), and a solid content of 2.95 parts by mass (solution: 9.93 parts by mass) of an alkali-soluble resin 1 (mixture of benzyl methacrylate/methacrylic acid copolymer, 30% PGMEA solution) and 165.3 parts by mass of PGMEA, mixed and dispersed by a bead mill (zirconium beads 0.3 mm diameter) for 3 hours . Then, the mixture liquid was further subjected to dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high pressure dispersing machine NANO-3000-10 (manufactured by NIHON BEECO., LTD.) equipped with a pressure reducing mechanism. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid P2. When the average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), the obtained blue pigment dispersion liquid P2 was 24 nm.

<Preparation of Blue Pigment Dispersion P3>

In the preparation of the above-described blue pigment dispersion liquid P2, a blue pigment dispersion liquid P3 was prepared in the same manner except that the following dispersant D1 was used as a dispersant instead of BYK-161.

[Chemical Formula 38]

The acid value of the dispersant D1 was 100 mgKOH/g. Further, the weight average molecular weight of the dispersant D1 was 20,000. Further, in the structure of the dispersant D1, the mass ratio of x and y was 50:50, and n was 20.

<Preparation of Blue Pigment Dispersion P4>

In the preparation of the blue pigment dispersion liquid P2 described above, the pigment dispersion liquid P4 was prepared in the same manner except that the following dispersant D2 was used as a dispersant.

[Chemical Formula 39]

The acid value of the dispersant D2 was 100 mgKOH/g. Further, the weight average molecular weight of the dispersant D2 was 20,000. Further, in the structure of the dispersant D2, the mass ratio of x and y was 15:85, and n was 20.

1-2. Preparation of colored curable composition

Each of the following components was mixed, dispersed, and dissolved to obtain a colored curable composition of each of Examples and Comparative Examples.・Dispersion of coloring agent (A) (the above-mentioned dispersions PA1 to PA46): 0.31 parts, solvent (PGMEA, cyclohexanone or cyclopentanone): 0.863 parts • Alkali-soluble resin (compounds of J1 or J2 described below) : 0.03 parts, dispersing agent (SOLSPERSE 20000: (1% cyclohexane solution, manufactured by LUBRIZOL JAPAN, LTD.): 0.125 parts ・ Photopolymerization initiator (compounds of C-5 or C-9 described below): 0.012 parts Blue pigment dispersion (the above-mentioned blue pigment dispersions P1 to P4) (pigment concentration: 13%): 0.615 parts, curable compound: 0.07 parts, surfactant (glycerol propanolate: (1% cyclohexane solution) 0.048 parts

Further, in Examples 15 and 23, a mixture of J1 and J2 (J1: J2 = 1:1 (mass ratio)) was used as the alkali-soluble resin.

Further, Examples 36 to 45 used a mixture of C-5 and C-9 (C-5: C-9 = 1:1 (mass ratio)) as a photopolymerization initiator.

<evaluation>

<<Spectral evaluation before and after development>>

A CT-4000L solution (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.; a transparent primer) was applied to a glass wafer so as to have a dry film thickness of 0.1 μm, and dried, and after forming a transparent film, at 220 Heat treatment at ° C for 5 minutes.

On the glass wafer on which the transparent film was formed, the colored curable composition was applied by a spin coater so that the dry film thickness was 0.6 μm, and heat treatment was performed for 120 seconds using a hot plate at 100 ° C (prebaking) grilled). Next, exposure was performed using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by CANON Inc.) at a wavelength of 365 nm and an exposure amount of 500 mJ/cm ² . Thereby, a color filter is obtained.

The color filter thus obtained was measured for transmittance in a wavelength range of 300 nm to 800 nm by a spectrophotometer (see: glass substrate) of an ultraviolet bondable near-infrared spectrophotometer UV3600 (manufactured by SHIMADZU Corporation).

The color filter after measuring the transmittance was placed on a horizontal rotary table of a rotary spray developing machine (Model DW-30, manufactured by CHEMITRONICS CO., LTD.), and CD-2000 (FUJIFILM ELECTRONIC MATERIALS CO., (manufactured by LTD.), paddle development was carried out at 23 ° C for 60 seconds. Next, the color filter was rotated at a number of revolutions of 50 r.p.m. by a rotating device, and pure water was supplied from a discharge nozzle in a shower form from above the center of rotation to perform a rinsing treatment, followed by spray drying. After the color filter was dried, the transmittance was measured again. The transmittance variation before and after development (the transmittance before development is T0 and the transmittance after development is T1, and the value represented by the formula |T0-T1|) is evaluated by the following criteria. A: The maximum variation of the transmittance before and after development is preferably less than 2% in the entire region of 300 nm to 800 nm. B: slightly better in the entire region of 300 nm to 800 nm, the maximum variation of the transmittance before and after development is 2% or more and less than 5% C: Fully in the entire region of 300 nm to 800 nm, the maximum variation of transmittance before and after development is 5% or more and less than 10%. D: Insufficient, the maximum transmittance before and after development in the entire region of 300 nm to 800 nm. The change value is 10% or more

<<Heat resistance evaluation>>

With respect to the color filter obtained above, the color difference (ΔE*ab value) before and after heating was measured with a colorimeter MCPD-1000 (manufactured by OTSUKA ELECTRONICS CO., LTD.), and the heat resistance was evaluated according to the following criteria. The color filter was placed on a hot plate at 200 ° C for 1 hour in contact with the surface of the wafer. A smaller median value of ΔE*ab indicates good heat resistance. In addition, the ΔE*ab value is a value obtained by the following color difference formula based on the CIE1976 (L*, a*, b*) spatial color system (Japanese Color Society, New Color Science Handbook (Showa 60) p. 266). The evaluation was performed on the basis of ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}1/2 or less. A: The value of ΔE*ab is 0 or more and less than 1.0 B: The value of ΔE*ab is 1.0 or more and less than 2.0 C: The value of ΔE*ab is 2.0 or more and less than 3.0 D: the value of ΔE*ab is 3.0 or more

<<Light resistance evaluation>>

The color filter obtained as described above was subjected to a light-resistant test apparatus (SX-75 manufactured by SUGA TEST INSTRUMENTS CO., LTD.) at a black panel temperature of 63 ° C, a quartz internal filter, and a 275 nm cut-off external filter. The light resistance test was carried out for 10 hours under the conditions of an illuminance of 75 mW/m ² (300 to 400 nm) and a humidity of 50%.

The color difference (ΔE*ab) before and after the light resistance test was measured with a spectrophotometer MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.). Based on the measured color difference (ΔE*ab), the light resistance was evaluated in accordance with the following evaluation criteria. It can be said that the smaller the value, the better the light resistance. A: The value of ΔE*ab is 0 or more and less than 1.0 B: The value of ΔE*ab is 1.0 or more and less than 2.0 C: The value of ΔE*ab is 2.0 or more and less than 3.0 D: the value of ΔE*ab is 3.0 or more

<<Dispersion stability evaluation>>

For the coloring-curable composition, the viscosity η1 (unit mPa·s) immediately after dispersion and the dispersion were measured at room temperature by an E-type viscosity meter (manufactured by TOKI SANGYO CO., LTD., RE-85L). The viscosity η2 (unit mPa·s) after leaving for 3 days at ° C, and the viscosity increase rate = (η2-η1) / η1 × 100 was calculated. Based on the calculated viscosity increase rate, the dispersion stability was evaluated in accordance with the following evaluation criteria.

The smaller the viscosity increase rate, the better the dispersion stability.

Evaluation was performed on the basis of the following criteria. A: The viscosity increase rate is 10% or less B: The viscosity increase rate is more than 10% and less than 20% C: The viscosity increase rate is more than 20%

[Table 4]

[table 5]

As shown in the above Tables 4 and 5, in the examples, the spectral variation before and after development was small, and a film excellent in light resistance can be formed. In addition, heat resistance is also excellent. Further, the colored curable composition of the examples was excellent in dispersion stability.

On the other hand, in the comparative example, the spectral fluctuation and the light resistance before and after the development cannot be simultaneously achieved.

The compounds shown in Tables 4 and 5 are as follows.

Alkali-soluble resin: the following structure

[Chemical Formula 40]

Photopolymerization initiator: the following structure

[Chemical Formula 41]

The sclerosing compound KAYARAD DPHA (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) NK ester A-DPH-12E (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) KAYARAD RP-1040 (NIPPON KAYAKU CO) , manufactured by LTD.) Multifunctional thiol compound (Chain-Transfer agent): the following structure

[Chemical Formula 42]

Epoxy compound E-1: EHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.

E-3: EPICLON N660 (manufactured by DIC CO., LTD.)

no

no

Claims (17)

A coloring curable composition comprising a coloring agent A having a structure represented by the following formula (1), a curable compound, and an organic solvent, wherein the coloring agent A is dispersed in the organic solvent. In the formula, R ¹ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 or -NHSO ₂ R ^X1 ; R ^X1 and R ^X2 each independently represent a hydrogen atom, Alkyl or aryl, R ¹¹ represents a sulfonic acid group or a bis(sulfonyl) fluorenylene group. The colored hardening composition according to claim 1, wherein in the colorant A, R ¹ , R ⁵ , R ⁶ and R ¹⁰ in the formula (1) are each independently an alkyl group. The colored hardening composition according to claim 1, wherein in the colorant A, R ¹ , R ⁵ , R ⁶ and R ^{10 of the} formula (1) are each independently a methyl group, an ethyl group or Isopropyl. The colored hardening composition according to any one of the preceding claims, wherein in the colorant A, R ¹¹ of the formula (1) is a sulfonic acid group, and R ² and R ^{3 are} R ⁴ , R ⁷ , R ⁸ and R ⁹ are a hydrogen atom. The colored hardening composition according to any one of the above-mentioned items, wherein the organic solvent is at least one selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent. The colored curable composition according to any one of the above-mentioned claims, further comprising a photopolymerization initiator, wherein the curable compound is a radically polymerizable compound. The color hardening composition according to any one of the items 1 to 3, further comprising an acidic dispersant having an acid value of 30 mgKOH/g or more. The colored hardening composition according to Item 7, which contains two or more kinds of the above-mentioned acidic dispersing agents. The color hardening composition according to any one of the items 1 to 3, further comprising a pigment having a phthalocyanine skeleton. The colored curable composition according to any one of the above-mentioned items of the present invention, further comprising a dye as a coloring agent other than the coloring agent A. The color hardening composition according to claim 10, wherein the dye is a dye having a skeleton selected from the group consisting of phthalocyanine, triarylmethane, and pyrromethylene. The color hardening composition according to any one of the items 1 to 3, which is used for a color filter. A color filter formed by using the color hardening composition according to any one of claims 1 to 12. A pattern forming method comprising the steps of: forming a colored curable composition layer on a support by using the colored curable composition according to any one of claims 1 to 12; The layer is exposed to a pattern; and the unexposed portion is removed by development to form a colored pattern. A method of manufacturing a color filter, comprising the pattern forming method according to claim 14 of the patent application. A solid-state imaging device having the color filter described in claim 13 of the patent application. An image display device having the color filter described in claim 13 of the patent application.