KR102002322B1 - Colored curable composition, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device - Google Patents

Abstract

The colored curable composition comprises a colorant A having a structure represented by formula (1), a curable compound, and an organic solvent, and the colorant A is dispersed in an organic solvent. R ¹ to R ¹⁰ each independently represent a hydrogen atom, an alkyl group or the like, and R ¹¹ represents a sulfonate group or a bis (sulfonyl) imide group.

Description

TECHNICAL FIELD [0001] The present invention relates to a color curable composition, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device. DISPLAY DEVICE}

The present invention relates to a colored curable composition, a color filter, a pattern forming method, a manufacturing method of a color filter, a solid-state image pickup device, and an image display device.

2. Description of the Related Art In recent years, the demand for solid-state image pickup devices such as charge coupled device (CCD) image sensors has been greatly increased due to the spread of digital cameras and mobile phones with cameras. Color filters are used as key devices for these displays and optical elements, and further demands for higher sensitivity and miniaturization are increasing. Such a color filter usually has three primary color patterns of red (R), green (G), and blue (B), and serves to decompose the transmitted light into three primary colors.

For example, Patent Documents 1 to 3 disclose the production of a color filter using an organic solvent-based coloring and curing composition containing a xanthine dye.

Patent Document 1: JP-A-2013-235257 Patent Document 2: JP-A-2012-207158 Patent Document 3: JP-A-2013-61619

In an organic solvent-based colored curable composition used for a color filter or the like, it is required that a cured film having small spectral fluctuation before and after development and having excellent light resistance is formed.

For example, light resistance is an important issue as a characteristic of a color filter, and there is a possibility that the spectroscopy of a color filter may fluctuate when the stability of the coloring agent as well as other materials is low. The inventors of the present invention have conducted extensive studies on the xanthine dye. As a result, it has been found that the N-alkylated xanthate tends to have low light resistance. For example, when a dispersant containing an amine is used, It was found that spectral fluctuations that would damage spectroscopy tend to occur.

Patent Documents 1 to 3 disclose a colored curable composition in which a xanthan gum is dispersed in an organic solvent. According to the study by the inventors of the present invention, however, the colored curable compositions disclosed in Patent Documents 1 to 3 have a problem that the dispersibility As a result, it was found that the xanthine dye dissolves in the developing solution, discoloration easily occurs after development, and the spectral fluctuation before and after development is large. Further, it was found that the light resistance was also poor.

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and it is an object of the present invention to provide a colored curable composition capable of forming a film having a small spectral fluctuation before and after development and having excellent light resistance. It is another object of the present invention to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device.

As a result of a detailed investigation, the present inventors have found that a colored curable composition comprising a colorant A which is a xanthene compound represented by the following formula (1), a curable compound, and an organic solvent and in which the colorant A is dispersed in an organic solvent , The present inventors have found that the above object can be achieved and have accomplished the present invention. The present invention provides the following.

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

[Chemical Formula 1]

Wherein 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 sulfonate group or a bis (sulfonyl) imide group.

<2> A coloring agent is, formula (1) R ^1, R ^5, R ⁶ and R ¹⁰ are, each independently, a colored curable composition according to an alkyl group of <1>.

<3> The coloring and curing composition according to <1>, wherein R ¹ , R ⁵ , R ⁶ and R ^{10 in the} formula (1) are each independently a methyl group, an ethyl group or an isopropyl group.

Of <4> coloring agent A, and the R ¹¹ in the formula (1) a sulfonate group, R ^2, R ^3, R ^4, R ^7, R ⁸ and R ⁹ is a hydrogen atom, a <1> to <3> A colored curable composition according to any one of the preceding claims.

<5> The colored curable composition according to any one of <1> to <4>, wherein the organic solvent is at least one selected from an ester solvent, an ether solvent, a ketone solvent and an alcohol solvent.

<6> The colored curable composition according to any one of <1> to <5>, wherein the composition further contains a photopolymerization initiator and the curable compound is a radically polymerizable compound.

<7> The colored curable composition according to any one of <1> to <6>, further comprising an acidic dispersant having an acid value of 30 mgKOH / g or more.

&Lt; 8 > The colored curable composition according to < 7 >, which contains two or more acid dispersing agents.

<9> The colored curable composition according to any one of <1> to <8>, further comprising a pigment having a phthalocyanine skeleton.

<10> The colored curable composition according to any one of <1> to <9>, which further contains a dye as a colorant other than the colorant A.

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

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

<13> A color filter comprising the colored curable composition according to any one of <1> to <12>.

<14> A method for producing a coloring-curable composition, comprising the steps of: forming a colored curable composition layer on a support using the colored curable composition according to any one of <1> to <12> And removing the development to form a colored pattern.

&Lt; 15 > A method for producing a color filter, comprising the pattern formation method according to < 14 >.

&Lt; 16 > A solid-state image pickup element having a color filter obtained by the color filter according to < 13 >, or the method for manufacturing a color filter according to < 15 >.

<17> An image display apparatus having a color filter according to <13> or a color filter obtained by the method for manufacturing a color filter described in <15>.

&Lt; 18 > A pigmented curable composition wherein the pigment having the phthalocyanine skeleton is C. I. Pigment Blue 15: 6.

<19> The colored curable composition according to <1>, wherein the content of the C. I. Pigment Blue 15: 6 is 100-200 parts by mass relative to 100 parts by mass of the colorant A.

According to the present invention, there is provided a colored curable composition, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device capable of forming a film having a small spectral fluctuation before and after development and having excellent light- .

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

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, light means an actinic ray or radiation. The term "actinic ray" or "radiation " means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray.

In the present specification, unless otherwise specified, the term " exposure "means not only exposure by a bright line spectrum of a mercury lamp, deep ultraviolet ray represented by an excimer laser, X-ray or EUV light, Is included in the exposure.

In the present specification, the numerical range indicated by using "~ " means a range including numerical values written before and after" ~ "as a lower limit value and an upper limit value.

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the colored curable composition.

In the present specification, the term "(meth) acrylate" refers to both or either of acrylate and methacrylate, "(meth) acryl" refers to both acrylate and methacrylate, The term "(meth) allyl" represents either or both of allyl and methallyl, and "(meth) acryloyl" represents either or both acryloyl and methacryloyl.

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 involved in the polymerization reaction.

In this specification, the term " process "is included in this term, not only in the independent process but also in the case where the scavenging action of the process is achieved even if it can not be clearly distinguished from other processes.

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 reduced values by Gel Permeation Chromatography (GPC) measurement.

In the present specification, the pigment means an insoluble coloring matter compound which is difficult to dissolve in a solvent. Typically, the pigment is dispersed in an organic solvent. Here, examples of the solvent include any solvent, and examples thereof include solvents exemplified in the column of the solvent to be described later. The pigment used in the present invention is preferably such that the dissolving amount of 100 g of propylene glycol monomethyl ether acetate at 23 DEG C and the dissolving amount of 100 g of water at 23 DEG C are all 0.1 g or less.

In the present specification, the dye means a dye compound which is easily dissolved in a solvent. Typically, the dye is present in the composition in a dissolved form of the dye compound. Here, examples of the solvent include any solvent, and examples thereof include solvents exemplified in the column of the solvent to be described later. The dye used in the present invention preferably has a dissolving amount of 2.0 g or more, for example, in 100 g of propylene glycol monomethyl ether acetate at 23 캜.

In this specification, unless otherwise stated, the ratio of the repeating unit in the compound having a repeating unit indicates a molar ratio.

&Lt; Coloring curable composition >

The colored curable composition of the present invention comprises a colorant A having a structure represented by the following formula (1), a curable compound, and an organic solvent, and the colorant A is dispersed in an organic solvent.

This colorant A is a solid, and further, has low solubility in an organic solvent. Therefore, it is possible to suppress discoloration after development, and to produce a color filter having small spectral fluctuation 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.

Further, since the coloring-curable composition of the present invention is dispersed in the organic solvent, the coloring agent A can suppress the sedimentation and aggregation of the coloring agent and is excellent in dispersion stability. Further, since the coloring agent A is hardly thermally diffused, a color filter excellent in heat resistance can be formed.

In the present invention, "colorant A is dispersed in an organic solvent" means that particles of the colorant A are present in a suspended or suspended state in an organic solvent. The fact that the coloring agent A is dispersed in the organic solvent can be confirmed by, for example, measuring the particle diameter distribution using the dynamic light scattering method.

Hereinafter, the present invention will be described in detail.

<< Colorant A >>

The colored curable composition of the present invention comprises a colorant A having a structure represented by the following formula (1).

(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 number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. The alkyl group may be straight chain, branched or cyclic, preferably straight-chain or branched. 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 monocyclic or polycyclic. The carbon number of the aryl group is preferably from 6 to 25, more preferably from 6 to 15, and still more preferably from 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.

In the formula (1), it is preferable that 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 the same group.

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

R ² and R ⁷ are preferably a hydrogen atom.

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

R ⁴ and R ⁹ 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 , and more preferably a hydrogen atom.

In the present invention, it is particularly preferable that R ² , R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms. According to this embodiment, an effect of increasing the absorbance per unit mass is obtained.

R ¹¹ represents a sulfonate group or a bis (sulfonyl) imide group. From the viewpoint of lowering solvent solubility, a sulfonate group is preferable.

Examples of the bis (sulfonyl) imide group include groups represented by the following formula (AN-1).

(3)

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

The halogen atom is preferably a fluorine atom.

The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group is preferably straight-chain or branched, more preferably straight-chain. As the alkyl group, a part of the hydrogen atoms is preferably substituted with a fluorine atom, and more preferably all of the hydrogen atoms are substituted with a fluorine atom. R group ¹⁰⁰ are shown are, and that the not all hydrogen atoms substituted with a fluorine atom, a carbon number of alkyl group of 1 to 10 (perfluoroalkyl group) are preferred, and more preferably a perfluoroalkyl group having from 1 to 4 carbon atoms, a methyl group, trifluoromethyl Is particularly preferable.

The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 14, and even more preferably from 6 to 10. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamido group and a nitro group, preferably a halogen atom or an alkyl group, Or an alkyl group is more preferable.

In the compound represented by the formula (1), the cations are non-gassed as follows, and the following structures are synonymous and all are included in the present invention.

[Chemical Formula 4]

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

[Chemical Formula 5]

In the above formulas, R ¹ to R ¹¹ are in agreement with the ranges described in the formula (1), and preferable ranges are also the same.

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

Specific examples of the colorant A include the following.

[Chemical Formula 6]

In the present invention, it is preferable that the colorant A has a low solubility in an organic solvent. Specifically, the amount of colorant A dissolved in 100 g of propylene glycol monomethyl ether acetate at 23 DEG C, the amount of colorant A dissolved in 100 g of cyclohexanone at 23 DEG C, and the amount of colorant A dissolved in 100 g of cyclopentanone at 23 DEG C It is preferable that any one of the amount of the coloring agent A dissolved is 1 g or less and that the amount of the coloring agent A dissolved in each organic solvent is 1 g or less.

In the present invention, it is preferable to use fine coloring agent A that has been finely divided. As a method of making the colorant A finer, for example, a method of preparing a liquid composition having a high viscosity together with the colorant A, an organic solvent and a water-soluble inorganic salt, and applying a stress to the resultant mixture using a wet pulverizer or the like.

Examples of the organic solvent include organic solvents to be described later. The amount of the organic solvent used in the micronization process is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the colorant A. [

Examples of the water-soluble inorganic salts include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like. The amount of the water-soluble inorganic salts to be used in the micronization process is preferably 1 to 50 parts by mass, more preferably 1 to 10 parts by mass, per 1 part by mass of the colorant A. [ Water-soluble inorganic salts having a water content of 1% or less are preferably used.

The operating conditions of the wet grinding apparatus in the step of finishing the colorant A are not particularly limited, but in order to effectively carry out the grinding by the grinding media, the operating condition in the case where the apparatus is a kneader is that the number of rotations of the blades in the apparatus is, 10 to 200 rpm is preferable, and a larger rotation ratio of the biaxial axis is preferable because the grinding effect is large. The operating time is preferably 1 to 8 hours in combination with the dry milling time, and the inner temperature of the apparatus is preferably 50 to 150 占 폚. The water-soluble inorganic salt which is a pulverizing medium has a particle size of 5 to 50 mu m and preferably has a sharp particle size distribution and a spherical shape.

In the colored curable composition of the present invention, it is preferable that the coloring agent A is present as particles in the composition. In particular, the average particle diameter (r) of the colorant A preferably satisfies 20 nm? R? 300 nm, preferably 25 nm? R? 250 nm, particularly 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 a high contrast ratio and a high light transmittance can be obtained. The "average particle diameter" used herein means the average particle diameter of the secondary particles aggregated by the primary particles of the colorant A (single crystals). The average particle size can be determined by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), counting 100 particle sizes in a portion where particles are not aggregated, and calculating an average value.

The secondary particle diameter distribution (hereinafter simply referred to as "particle diameter distribution") of the colorant A that can be used in the present invention is such that the secondary particles contained in the (average particle diameter ± 100) nm are not less than 70% It is preferably at least 80% by mass. In the present invention, the particle size distribution was measured using the scattering intensity distribution.

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

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

One kind of colorant A may be used. In addition, R ¹ to R ^{11 in} the general formula (1) may include two or more compounds of different combinations. When two or more of them are contained, it is preferable that the total amount is in the above range.

<< Other coloring agents >>

The color-curable composition of the present invention may contain a coloring agent other than the above-mentioned coloring agent A, and preferably contains another coloring agent. The other coloring agent may be either a dye or a pigment, or both of them may be used in combination. One kind of the other coloring agents may be used, or two or more kinds thereof may be used.

As the pigment, various conventionally known inorganic pigments or organic pigments can be mentioned. In view of the fact that the inorganic pigment or the organic pigment is preferably a high transmittance, it is preferable to use a pigment having an average particle size as small as possible. Considering handling properties, the average particle size of the pigment is preferably 0.01 to 0.1 mu m , And more preferably 0.01 to 0.05 mu m.

Specific examples of the inorganic pigments include black pigments such as carbon black and titanium black; pigments such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium , Metal oxides such as zinc and antimony, and complex oxides of the above metals.

Examples of organic pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited thereto.

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, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 172, 173, 174, 175, 169, 170, 171, 172, 173, 174, 148, 150, 151, 152, 153, 154, 155, 156, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213,

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

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 175, 176, 177, 178, 179, 170, 176, 168, 169, 170, 171, 172, 175, 176, 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

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 various combinations in order to enhance color purity.

Among them, a pigment having phthalocyanine skeleton (also called phthalocyanine pigment) is preferable, and C. I. Pigment Blue 15: 6 is more preferable.

As the dyes, for example, Japanese Unexamined Patent Publication No. 64-90403, Japanese Unexamined Patent Publication No. 64-91102, Japanese Unexamined Patent Publication No. 1-94301, Japanese Unexamined Patent Publication No. 6-11614, Japanese Patent No. 2592207 , U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 5,05950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, A dye disclosed in JP-A-6-194828 can be used. As a chemical structure, it is possible to use a pyrazole compound, a pyromethene compound, an anilino compound, a triphenylmethane compound, an anthraquinone compound, a benzilidene compound, an oxolin compound, a pyrazolotriazoazo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

In the present invention, the dye is preferably a dye having a skeleton selected from phthalocyanine, triarylmethane and pyromethene, more preferably a phthalocyanine skeleton or a triarylmethane skeleton, A dye having a phthalocyanine skeleton is more preferable. By including these dyes, the dispersibility of the above-mentioned colorant A in the composition can be improved. Further, the heat resistance and the light resistance are improved.

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

The formula (F)

(7)

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

Rp Rp ₁ ~ ₁₆ are, each independently, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^{X1, X1} -SR, -COR ^{X1, X1} -COOR, -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 a represents, R ^X1 and R ^X2 are, each independently, represent a hydrogen atom, an alkyl group, or aryl group, M ² is a quaternary ammonium cation, a divalent metal atom, a monovalent metal atom such as sodium, lithium, potassium For example, Mg, Ca, Zn, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni and Co. In view of excellent spectroscopy, a compound represented by the following formula (F-1) is particularly preferable.

The formula (F-1)

[Chemical Formula 8]

In the formula (F-1), M ¹ represents a metal atom or a metal compound. Expression of the M ¹ (F-1) is an M ¹ with the consent of the formula (F), it is also the same preferable range.

In 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. The alkyl group is preferably straight-chain or branched. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include an aryl group, an alkoxy group, an allyloxy group, an aryloxy group, and a halogen atom.

The aryl group represented by R ^a and R ^b may be monocyclic or polycyclic. The number of carbon atoms is preferably from 6 to 25, more preferably from 6 to 15, and still more preferably from 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. Examples of the substituent include an alkyl group, an alkoxy group, an allyloxy group, and a halogen atom.

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

n represents an integer of 1 to 10, preferably 1 to 5;

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

Specific examples of phthalocyanine dyes include, for example, the following compounds, and compounds described in International Publication No. WO2009 / 119364, paragraphs 0044 to 0059.

[Chemical Formula 9]

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

Equation (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 is a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ shows the (Rtp ⁹ and Rtp ¹⁰ represents 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 an integer of 0 to 4; When a, b and c are two or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be connected to form a ring. X ^- represents an anionic structure.

In the formula (TP), examples of the anion structure represented by X ^- include a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methide anion, ^{anion, -CON - CO-, -CON - SO} 2 -, BF 4 -, PF 6 -, SbF 6 -, B - (CN) 3 is preferably at least one member selected from OCH _3. More preferably, a sulfonic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methide anion, a carboxylic acid anion, a tetraarylborate anion, BF ₄ ^- , PF ₆ ^- , And SbF ₆ ^- .

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 a hydrogen atom or NRtp ⁹ Rtp ¹⁰ are preferred, 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 each independently a straight or branched alkyl group of 1 to 5 carbon atoms, an alkenyl group of 1 to 5 carbon atoms, an aryl group of 6 to 15 carbon atoms, a carboxyl group, More 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, and Rtp ⁷ is preferably an alkenyl group (particularly preferably a phenyl group to which two adjacent alkenyl groups are connected), a phenyl group or a carboxyl group.

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

Specific examples of the triarylmethane dyes include the following compounds, and the compounds described in paragraphs 0176 to 0177 of Japanese Laid-Open Patent Publication No. 2014-186342.

(11)

A dye having a pyrromethene skeleton (also referred to as a pyrromethene dye) includes, for example, a compound represented by the following formula (PM).

Expression (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 arylamino group. R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group, an alkenyl group or an aryl group, and an alkyl group is particularly preferable.

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 preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitryl group, an imide group, or a carbamoylsulfonyl group, An aryloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitryl group, an imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitryl group, , And a carbamoyl sulfonyl group is more preferable.

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. R ¹⁷ is preferably a hydrogen atom.

And Ma represents a metal atom or a metal compound. Examples of the metal atom or the metal compound include those described in Formula (F), and Zn, Cu, Co, or V = O is preferable, and Zn is more preferable.

X ² and X ³ are each independently NR ^{x wherein} R ^x represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, a nitrogen atom, Sulfur atom. X ² and X ³ are preferably oxygen atoms.

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

X ¹ represents a group capable of bonding with Ma. X ¹ may be any of a group capable of binding to Ma, specifically, water, alcohols (e.g. methanol, ethanol, propanol), etc., and also "metal chelate" ([1] (2) (1996), [3] (1997), etc.). Among them, water, a carboxylic acid compound and an alcohol are preferable from the viewpoint of production, and water and a carboxylic acid compound are more preferable.

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

Examples of the pyrromethene 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, more preferably 0.1 to 15 parts by mass, and most preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the colorant A The mass addition is more preferred.

The content of the phthalocyanine pigment is preferably 80 to 300 parts by mass, more preferably 90 to 250 parts by mass, and further preferably 100 to 200 parts by mass, per 100 parts by mass of the colorant A. [ Within this range, the effect of excellent spectroscopy can be obtained. The phthalocyanine pigments may be of one kind alone or in combination of two or more kinds. When two or more kinds are used in combination, it is preferable that the total is in the above range.

The content of the dye is preferably from 1 to 30 parts by mass, more preferably from 1 to 25 parts by mass, and still more preferably from 1 to 20 parts by mass, per 100 parts by mass of the colorant A. When the content of the dye is within the above range, the dispersibility of the colorant A is improved and the dispersion stability of the colored curable composition is more excellent. The dye may be of only one type, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total is in the above range.

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

<< Curing compound >>

The colored curable composition of the present invention contains a curable compound. As the curable compound, a known compound that can be crosslinked by radicals, acids, or heat can be used. For example, a compound having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group, or the like can be given. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

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

In the present invention, the radical polymerizable compound (hereinafter also referred to as a polymerizable compound) may be any of a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, It is acceptable.

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

Examples of the monomer and the prepolymer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides and oligomers thereof, Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, a reaction product of a monofunctional or polyfunctional alcohol, an amine, a thiol, a halogen or a tosyloxy group Also suitable are unsaturated carboxylic acid esters or amides having a cleavable substituent and reacting with monofunctional or polyfunctional alcohols, amines and thiols. It is also possible to use a group of compounds substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like in place of the above unsaturated carboxylic acid.

As specific compounds of these compounds, compounds described in paragraphs [0095] to [0108] of JP-A No. 2009-288705 can be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound having at least one group having an ethylenic unsaturated bond and having a boiling point of 100 캜 or more at normal pressure is also preferable. As an example thereof, reference can be made to the compounds described in paragraphs 0227 and 0225 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970, the contents of which are incorporated herein by reference.

Examples of the polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available as Kayarad D-320; Acrylate (commercially available from KAYARAD D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available from Kaya Co., Ltd.) A-DPH-12E manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Kagaku Co.), and a structure in which these (meth) acryloyl groups intervene between ethylene glycol and propylene glycol moieties For example, SR454, SR499 commercially available from Satomaru Co., Ltd.). These oligomer types can also be used. In addition, Kayarad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) may be used.

Preferred embodiments of the polymerizable compound are 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 aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid are preferable, and a polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride And particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mg KOH / g, particularly preferably from 5 to 30 mg KOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if 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.

The polymerizable compound is also a preferred embodiment of the compound having a caprolactone structure.

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 trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta (Meth) acrylic acid and? -Caprolactone obtained by esterifying a polyhydric alcohol such as trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, (Meth) acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 14]

In the general formula (Z-1), all six R's are groups represented by the following general formula (Z-2), or 1 to 5 of the six R's are groups represented by the following general formula (Z-2) And the remainder is a group represented by the following general formula (Z-3).

[Chemical Formula 15]

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

[Chemical Formula 16]

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

The polymerizable compound having a caprolactone structure is commercially available, for example, as a Kayarad DPCA series from Nippon Kayaku. DPCA-20 (in the formulas (Z-1) to (Z-3) 1, the number of groups represented by the formula (Z-2) = 2, and R ¹ are all hydrogen atoms), DPCA-30 , A compound in which R ¹ is a hydrogen atom), DPCA-60 (the compound represented by the formula: m = 1, the number of groups represented by the formula (Z-2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 M = 2 in the same formula, the number of groups represented by the formula (Z-2) = 6, and R ¹ are all hydrogen atoms).

The polymerizable compound may be a compound represented by the following general formula (Z-4) or (Z-5).

[Chemical Formula 17]

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

In the general formula (Z-4), the sum of the (meth) acryloyl groups is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

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

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

The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

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

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

- ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (Z-4) or the general formula (Z- Side is bonded to X is preferable.

The compounds represented by the general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the general formula (Z-5), all of the six X's are preferably acryloyl groups.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to a ring opening skeleton And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride to the terminal hydroxyl group of the ring opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

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

Specifically, the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplified compounds (a) to (f)") (e) and (f) are preferable.

[Chemical Formula 18]

[Chemical Formula 19]

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include compounds described in Japanese Patent Publication No. 48-41708, JP-A-51-37193, JP-A-2-32293, The ethylene oxide skeleton disclosed in Japanese Patent Publication No. 58-49860, Japanese Examined Patent Publication No. 56-17654, Japanese Examined Patent Publication No. 62-39417, Japanese Examined Patent Publication No. 62-39418, Lt; / RTI &gt; are also suitable. Further, addition polymerizable compounds having an amino structure or sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, , A colored curable composition having a very high photosensitive speed can be obtained.

(Commercially available from Shin-Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

<<< Compound having an epoxy group >>>

In the present invention, a compound having an epoxy group may be used as the curing compound.

When a pattern is formed by a dry etching method, a compound having an epoxy group is preferably used as a curable compound.

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

The compound having an epoxy group in the present invention is preferably a compound having a structure in which two benzene rings are connected to each other through hydrocarbon groups. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

The epoxy group is preferably connected through a linking group. Examples of the linking group include a structure represented by an alkylene group, an arylene group, -O-, -NR'- (wherein R 'represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent and preferably a hydrogen atom) -SO ₂ -, -CO-, -O-, and -S-.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of a compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, further preferably 100 to 300 g / eq Do.

The compound having an epoxy group may be a low molecular weight compound (for example, having a molecular weight of less than 2000, and more preferably, a molecular weight of less than 1000), and may be a macromolecule (for example, a molecular weight of 1000 or more, Or more). The weight-average molecular weight of the compound having an epoxy group is preferably 200 to 100000, more preferably 500 to 50,000.

The compound having an epoxy group can be prepared by reacting a compound described in paragraphs Nos. 0034 to 0036 of JP-A No. 2013-011869, paragraphs 0147 to 0156 of JP-A No. 2014-043556, paragraph No. 0085 to 0092 of JP-A No. 2014-089408 May be used. These contents are hereby incorporated by reference.

Examples of commercially available products include "EHPE3150, manufactured by Daicel Chemical Industries, Ltd." and "EPICLON N660 (manufactured by DIC Corporation)".

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 more preferably 0.5% by mass or more, for example, and further preferably 1% by mass or more. The upper limit is more preferably 30 mass% or less, for example, and still more preferably 20 mass% or less. The curing compound may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, it is preferable that the total amount is in the above range.

<< Multifunctional Thiol Compounds >>

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 and the like. The polyfunctional thiol compound is preferably a secondary alkene thiol compound, particularly preferably a compound having a structure represented by the following general formula (T1).

The general formula (T1)

[Chemical Formula 20]

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

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

[Chemical Formula 21]

When 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, more preferably 0.8 to 6.4% by mass, based on the total solid content of the colored curable composition . The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<< Organic solvents >>

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

The organic solvent is not particularly limited if it satisfies the solubility of each component and the application property of the colored curable composition, but it is preferably selected in consideration of solubility, application property and safety of each of colorants, resins, curable compounds, etc. . Among them, at least one kind selected from an ester solvent, an ether solvent, a ketone solvent and an alcohol solvent is preferable from the viewpoint of the dispersibility of the colorant A described above. One kind of the organic solvent may be used, or two or more kinds of them may be mixed and used. In the present invention, the term " ether solvent "means a solvent containing an ether bond, and the term" ester solvent " means a solvent containing an ester bond and the term "ketone solvent" That is, for example, an alcohol solvent containing an ether bond is also an "ether solvent" and an "alcohol solvent". The solvent having an ether bond and an ester bond is also an " ether solvent " and an "ester solvent ".

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, Propyleneglycol diacetate, 1,3-butyleneglycol monoacetate, propyleneglycol diacetate, propyleneglycol diacetate, propyleneglycol monoacetate, propyleneglycol diacetate, propyleneglycol diacetate, propyleneglycol diacetate, 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 Ethane acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Diethyleneglycol monomethyl ether acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, methyl methoxyacetate, Methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, Methyl ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutylacetate and 3-methyl-3-methoxybutylacetate .

As the ether solvent, a solvent having an ether bond, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol monoalkyl ethers such as ethers; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl 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 ethyl methyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, and the like Diethylene glycol dialkyl ethers; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Phenol ethers such as anisole, phenetole, methyl anisole and the like; 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol and the like.

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

As the alcohol solvent, among the above-mentioned solvents, those which are alcohol, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like can be mentioned.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably substantially no peroxide.

In the present invention, the solubility parameter (SP) value of the organic solvent is preferably 15 to 25 (MPa) ^1/2 , more preferably 19 to 23 (MPa) ^1/2 . The SP value is a value obtained by the Hoy method in the present invention. As a reference of the Hoi method, HL Hoi: J. Paint Tech., 42 (540), 76-118 (1970), and the SP value basis, application and calculation method (Yamamoto, .

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

The colored curable composition of the present invention may contain only one kind of organic solvent or two or more kinds of organic solvents. When two or more kinds are included, the total amount is preferably in the above range.

<< Resin >>

The colored curable composition of the present invention preferably contains a resin. Resins are used, for example, for dispersing a colorant in a composition and for use as a binder. The resin mainly used for dispersing a coloring agent such as a pigment is also referred to as a dispersing agent. However, such use of the resin is merely an example, and the resin may be used for other purposes.

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

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

In the colored curable composition of the present invention, the proportion of the acid resin in the total mass of the resin is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and still more preferably 70 to 100 mass%.

<<< Dispersant >>>

In the present invention, the colored curable composition preferably contains a dispersant. Examples of the dispersant include an acidic dispersant (acid resin) and a basic dispersant (basic resin).

The dispersant preferably contains at least an acidic dispersant, more preferably an acidic dispersant. By including at least the dispersing agent in an acidic dispersing agent, generation of needle-like foreign matter can be suppressed more effectively. In addition, the dispersibility of the colorant is improved, and unevenness in brightness is less likely to occur. Further, since excellent developability is obtained, pattern formation can be appropriately performed by photolithography. 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, for example, when the dispersant is an acidic dispersant alone.

Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is larger than the amount of basic groups. The acid dispersing agent (acidic resin) is preferably a resin having an acid value of 70 mol% or more when the total amount of the acid group and the basic group is 100 mol%, more preferably a resin consisting essentially of an acid group . The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.

The basic dispersant (basic resin) refers to a resin in which the amount of the basic group is larger than that in the acid group. The basic dispersant (basic resin) is preferably a resin in which the amount of the basic group accounts for not less than 50 mol% when the total amount of the acid group and the basic group is 100 mol%. The basic group of the basic dispersant is preferably an amine.

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

In the present invention, the content of the dispersing agent is preferably 100 to 500 parts by mass, more preferably 150 to 400 parts by mass, per 100 parts by mass of the colorant A described above.

In the present invention, the dispersant may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable to use two or more kinds of acidic dispersing agents in combination. According to this embodiment, the dispersion stability of the composition can be improved.

Examples of the dispersing agent include polymer dispersing agents such as polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalenesulfonic acid-formalin condensate], polyoxyethylene alkylphosphoric acid ester, 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 based on the structure. The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent re-aggregation. Therefore, a terminal modified polymer, graft-type polymer, and block-type polymer having an anchor site on the surface of the pigment are preferable structures.

Examples of the end-modified polymer include polymers having a phosphate group at the terminals described in JP-A-3-112992 and JP-A-2003-533455, sulfonic acid groups at the terminals described in JP-A-2002-273191, A polymer having a partial skeleton of an organic dye or a heterocycle described in JP-A-9-77994, and the like. Furthermore, a polymer having an anchor site (an acid group, a basic group, a partial skeleton of an organic dye, a heterocycle, etc.) introduced into two or more pigment surfaces at the polymer terminal end described in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

As the graft-type polymer, for example, a polyester-based dispersant and the like can be given. Specifically, the reaction product of a poly (lower alkyleneimine) and a polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, A reaction product of a polyallylamine and a polyester described in Japanese Patent Application Laid-Open No. 9-169821, a macromonomer described in JP-A-10-339949, JP-A-2004-37986 and WO2010 / 110491, A graft polymer having a partial skeleton of an organic dye or a heterocycle described in JP-A-2003-238837, JP-A-2008-9426 and JP-A-2008-81732, etc., a copolymer of a nitrogen atom monomer, A copolymer of an acid group-containing monomer and a macromonomer described in Japanese Unexamined Patent Publication No. 2010-106268, and an amphoteric copolymer having a basic group and an acid group described in JP-A-2009-203462 And the like.

Known macromonomers can be used as the macromonomers used when the graft polymer is produced by radical polymerization. Macromonomer AA-6 (polymethacryloylmethyl group whose terminal group is a methacryloyl group) manufactured by DOKOSEI CO., LTD. , AN-6S (a copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (poly (meth) acrylate having a terminal group of methacryloyl group), AS-6 (polystyrene in which the terminal group is methacryloyl group) Butyl acrylate), Flaccel FM5 (5-molar equivalent of 2-hydroxyethyl methacrylate-epsilon -caprolactone) manufactured by Daicel Chemical Industries, Ltd., FA10L (? -Caprolactone of 2-hydroxyethyl acrylate 10 molar equivalents of lactone), and polyester-based macromonomers described in JP-A-2-272009.

As block type polymers, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

The resin used as the dispersing agent preferably contains a repeating unit having an acid group. By including the repeating unit having an acid group, the resin can further reduce the residues generated in the base of the colored pixel when the colored pattern is formed by photolithography.

The repeating unit having an acid group can be formed using a monomer having an acid group. Examples of the monomer derived from an acid group 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, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, Caprolactone mono (meth) acrylate, and the like. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of the carboxyl group. Among them, from the viewpoint of developing removability of the unexposed portion, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride Is preferred.

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

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

As the repeating unit having an acid group, reference can be made to the description of paragraphs 0067 to 0069 of Japanese Laid-Open Patent Publication No. 2008-165059, the contents of which are incorporated herein.

In the present invention, a graft copolymer containing repeating units represented by any one of formulas (A1) and (A2) and repeating units having an acid group can be used as the dispersing agent. This graft copolymer can be used as an acidic dispersant.

[Chemical Formula 22]

In the general formula (A1) and ^{(A2), R 1 ~ R} 6 are, each independently, represents a hydrogen atom, or a monovalent organic, X ¹ and X ² are, each independently, -CO-, -C ( -O-, -CONH-, -OC (= O) -, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, A ¹ and A ² are, each independently, represents a monovalent organic group, m and n are, each independently, an integer of 2 ~ 8, p and q are each independently 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 preferable. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

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

X ¹ and X ² each independently represent -CO-, -C (= O) O-, -CONH-, -OC (= O) - or a phenylene group. Among them, -C (= O) O-, -CONH- and phenylene groups are preferable from the viewpoint of adsorption to pigments, and -C (= O) O- is most preferable.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group having an alkylene group and a partial structure containing a hetero atom or a hetero atom.

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 particularly preferably an alkylene group having 1 to 4 carbon atoms.

The hetero atom in the partial structure containing a hetero atom includes, for example, an oxygen atom, a nitrogen atom and a sulfur atom, and among these, an oxygen atom and a nitrogen atom are preferable.

Examples of the divalent organic linking group include a partial structure containing a hetero atom or a hetero atom selected from -C (═O) -, -OC (═O) -, -NHC (═O) - at the terminal of the aforementioned alkylene group And is bonded to an adjacent oxygen atom through a partial structure containing a hetero atom or a hetero atom is preferable from the viewpoint of adsorption to the pigment. Here, the adjacent oxygen atom is, for L ² in the formula (A1) L ^1, and the formula (A2) in the means of oxygen atoms bonded on the side chain terminal side.

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 preferable. Examples of the substituent include the substituents described in Japanese Patent Laid-Open Publication No. 2009-256572, paragraph number 0028, the contents of which are incorporated herein by reference.

As A ¹ and A ² , a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms are preferable from the viewpoints of dispersion stability and developability, More preferably a straight chain alkyl group having from 4 to 15 carbon atoms, a branched alkyl group having from 4 to 15 carbon atoms and a cyclic alkyl group having from 6 to 10 carbon atoms, more preferably a straight chain alkyl group having from 6 to 10 carbon atoms, a branched chain having from 6 to 12 carbon atoms An alkyl group is more preferred.

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

p and q each independently represent an integer of 1 to 100; The other of p and the other of q may be mixed with two or more kinds. p and q are preferably from 5 to 60, more preferably from 5 to 40, and still more preferably from 5 to 20, from the viewpoints of dispersion stability and developability.

For details of the repeating unit represented by the general formula (A1) and the repeating unit represented by the general formula (A2), reference may be made to the description of paragraphs 0060 to 0084 of Japanese Laid-Open Patent Publication No. 2012-173356, .

As the repeating unit having an acid group, the repeating unit described above may be mentioned.

For details of the graft copolymer, reference may be made to paragraphs 0060 to 0109 of Japanese Laid-Open Patent Publication No. 2012-173356, the contents of which are incorporated herein by reference. Specific examples of the graft copolymer include, for example, the following.

(23)

In the present invention, as the dispersing agent, an oligoiminic resin containing a nitrogen atom in at least one of the main chain and the side chain can be used. The oligoimine resin preferably has a repeating unit having a partial structure X having a functional group having _a pK _{a of} 14 or less and a side chain containing an oligomer chain or a polymer chain Y of 40 to 10,000 atoms and having at least one of a main chain and a side chain Resins having a basic nitrogen atom are preferred.

Here, the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom showing basicity. The oligomeric resin preferably contains a structure having a nitrogen atom with a base strength pK _{b of} 14 or less and more preferably contains a structure having a nitrogen atom of pK _b 10 or less.

Base strength pK _b in the present invention is, to say the pK _b of the temperature 25 ℃, is one of the indicators for indicating the strength of the base to quantitatively, basicity constants and accept. The base strength pK _b and the acid strength pK _a described later are in the relationship of pK _b = 14-pK _a .

The oligomeric resin may be a poly (lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a poly (diallylamine) repeating unit, a metaxylene diamine-epichlorohydrin polycondensate repeating unit, and a poly (I) a repeating unit having a basic nitrogen atom and having a partial structure X bonded to a basic nitrogen atom and having a functional group having _a pK _{a of} 14 or less and (ii) a repeating unit (Ii) comprising an oligomer chain having 40 to 10,000 atoms or a polymer chain Y is particularly preferable.

The poly (lower alkyleneimine) may be in the form of a chain or a network. Herein, in the present invention, the lower alkyleneimine means an alkyleneimine containing an alkylene chain of 1 to 5 carbon atoms.

It is preferable that the repeating unit (i) forms a main chain portion in the oligomeric resin. The number average molecular weight of the oligomeric resin excluding the side chain (ii) is preferably 100 to 10,000, more preferably 200 to 5,000, and most preferably 300 to 2,000, . The number average molecular weight of the main chain portion can be determined from the ratio of the integral value of hydrogen atoms in the terminal group to the main chain portion as measured by nuclear magnetic resonance spectroscopy or can be obtained by measuring the molecular weight of an oligomer or polymer containing an amino group as a raw material.

One preferred embodiment of the oligomeric resin includes a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the general formula (I-2).

&Lt; EMI ID =

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

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

(25)

In the general formula ^{(I-3), R 1} , R 2 , and a is R ^1, R ² and a and agreed in the formula (I-1). Y 'represents an oligomer chain or polymer chain having 40 to 10,000 atoms having an anionic group. The repeating unit represented by the general formula (I-3) can be formed by reacting a resin having a primary or secondary amino group in the main chain portion with an oligomer or polymer having a group capable of reacting with an amine to form a salt .

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

The oligomeric resin may contain, in addition to the repeating units represented by the general formula (I-1), the general formulas (I-2) and (I-3), a lower alkyleneimine containing a primary or tertiary amino group It may be included as a repeating unit. However, the nitrogen atom in the lower alkyleneimine repeating unit may further be 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 1 to 80 mol%, and most preferably 3 to 50 mol%, of the total repeating units contained in the oligomeric resin.

The repeating unit represented by the general formula (I-2) is preferably contained in an amount of 10 to 90 mol%, and most preferably 30 to 70 mol%, of all the repeating units contained in the oligomeric resin.

The content ratio [(I-1) :( I-2)] of the repeating unit (I-1) and the repeating unit (I-2) 1: 100, and more preferably in the range of 1: 1 to 1:10.

The repeating unit represented by the general formula (I-3) which is used in combination according to purposes has a structure in which a partial structure containing an oligomer chain or a polymer chain Y 'having 40 to 10,000 atoms is ionically bonded to the nitrogen atom of the main chain And is preferably contained in an amount of 0.5 to 20 mol%, and most preferably in an amount of 1 to 10 mol%, from the viewpoint of the effect of all the repeating units contained in the oligomeric resin. The fact that the polymer chain Y 'is ionically bonded can be confirmed by infrared spectroscopy or base titration.

The oligomeric resin may be a compound described in Japanese Patent Laid-open Publication No. 2009-258668, paragraphs 0016 to 0018, and Japanese Patent Laid-Open Publication No. 2009-203462, paragraphs 0021 to 0080. These contents are hereby incorporated by reference.

In the present invention, as the acidic dispersant, a resin having an acid group and an unsaturated double bond described in paragraphs 0020 to 0075 of JP-A No. 2008-165059 can be used.

Specific examples of such a dispersant are DA-7301 manufactured by Gusumoto Kasei Co., Ltd., DISPER BYK-101 (polyamide amine phosphate) manufactured by Big Chemie Co., 107 (carboxylic acid (A copolymer containing an acid group), 111 (a phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 171, 174, 176, 180, 182, EFKA 4047, 4050 to 4010 to 4165 (polyurethane-based), EFKA 4330 to 4340 (block copolymer), " BYK-6919 ", " (Fatty acid polyesters), 6745 (phthalocyanine derivatives), 6750 (azo pigment derivatives), "and " PB101, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (uretene oligomer) "manufactured by Kyowaisha Chemical Co., 873, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", "Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- , "Acetamine 86 (Stearylamine Acetate)", "Nippon Lubrizol Co., Ltd.", "Solpres 5000" (manufactured by Nippon Polyurethane Industry Co., Ltd.), "Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) (Graft polymer), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having functional part at the terminal part), 24000, 28000, 32000, 38500 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd.," Hinoact T-8000E "manufactured by Kawaken Fine Chemicals Co., Etsu , "Oganosiloxane polymer KP341" manufactured by Kugo Kogyo Co., Ltd., "W001: cationic surfactant" manufactured by YUSHO CO., LTD., Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl Nonionic surfactants such as ethers, polyoxyethylene octylphenyl ethers, polyoxyethylene nonylphenyl ethers, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters; "W004, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", and " EFKA Polymer 450 "manufactured by Morishita Sangyo Co., Disperse AID 6, Disperse Aid 8, Disperse Aid 15, Disperse A 9100 "manufactured by Adeka Co., Ltd., Adeka Pluronic L31, F38, L42 manufactured by Adeka Co., , L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- ) And the like can be given the "EO net (trade name) S-20". It is also possible to use Acribe FFS-6752, Acribe FFS-187, ARC Liqueur RD-F8, and Cyclamer P.

The resin described in the above-mentioned dispersant may be used for purposes other than the dispersant. For example, it may be used as a binder.

<<< Alkali-soluble resin >>>

The colored curable composition of the present invention may contain an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formation property are improved. The alkali-soluble resin may also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000.

The alkali-soluble resin may be a linear organic polymer or may be appropriately selected from among alkali-soluble resins having at least one group capable of promoting alkali solubility in a molecule (preferably, acrylic copolymer, styrene-based copolymer as a main chain) have.

The alkali-soluble resin is preferably a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance, , An acrylamide resin, and an acrylic / acrylamide copolymer resin.

Examples of the group capable of promoting 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. Examples thereof include those soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid is particularly preferable. These acid groups may be only one kind, or two or more kinds.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent at the time of producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally .

As the alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, Soluble resin such as an alkali-soluble phenol resin such as a phenol resin, an acidic cellulose derivative having a carboxyl group in the side chain, and an acid anhydride added to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomer copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like as the N-substituted maleimide monomer described in JP-A No. 10-300922 , N-phenylmaleimide, N-cyclohexylmaleimide and the like. The other monomers copolymerizable with the (meth) acrylic acid may be one type or two or more types.

In order to improve the crosslinking efficiency of the color-curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. The 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 may be prepared by reacting an isocyanate group and a hydroxyl group in advance to prepare a compound (a) containing a polymerizable group such as a (meth) acryloyl group and leaving one unreacted isocyanate group And an urethane-modified alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group; An alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; Acid pendant epoxy acrylate resins; An alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; An alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a compound having an isocyanate and a polymerizable group; A resin obtained by subjecting a resin having an ester group on the side chain to a? -Position or an? -Olefin atom or a sulfonate group on? On the? Side described in JP-A-2002-229207 and JP-A-2003-335814 by a basic treatment Alkali-soluble resins and the like are preferable.

Examples of the alkali-soluble resin containing a polymerizable group include a dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), a photomer 6173 (COOH-containing polyurethane acrylic oligomer, Diamond Shamrock Co., (All manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series (for example, ACA230AA), and Plaxcel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Viscoat R- Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) and ARC Liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

The alkali-soluble resin is preferably a copolymer of benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2- hydroxyethyl / (Meth) acrylic acid / other monomers can be preferably used. Also, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate and a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / 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 / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

The alkali-soluble resin is obtained by polymerizing a monomer component comprising a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may also be referred to as " It is also preferable to include the polymer (a).

(26)

In the general 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.

(27)

In the general 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), reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2010-168539.

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 includes, for example, methyl, ethyl, n-propyl, Butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl, and other straight or branched alkyl groups; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Isopropyl) -2,2 '- [oxybis (methylene)] - propenoate, di (n-propyl) -2,2' - [oxybis Di (isobutyl) -2,2 '- [oxybis (2-methoxyphenyl) -2,2'- Methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '- [oxybis Di (lauryl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Methoxyethyl) -2,2 '- [oxybis (meth) 2-propenoate, dibenzyl-2, 2 '- [oxy (2-methoxyphenyl) Bis (methylene)] bis-2-propenoate, diphenyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- )] Bis-2-propenoate, dicyclohexylcyclohexyl) -2,2 '- [oxybis (methylene)] bis- , 2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2' Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamantyl- 2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

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

(28)

In 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 an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring . n represents an integer of 1 to 15;

In the formula (X), the number of carbon atoms of the alkylene group of R ₂ is preferably 2 to 3. 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 include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (isopropyl) group.

The alkali-soluble resin can be referred to the description of Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to US Patent Application Publication No. 2012/0235099, <0685> to [0700]), Quot;

In addition, the copolymer (B) described in paragraphs Nos. 0029 to 0063 described in JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the copolymer described in paragraphs 0088 to 0098 of JP-A- The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resin used in the examples of Japanese Laid-Open Patent Publication No. 2013-024934 To 0143 and binder resins used in the examples, the binder resins described in paragraphs 0092 to 0098 of JP-A No. 2011-242752 and the binder resins used in the examples, JP-A-2012-032770 The binder resin described in paragraphs [0030] to [0072] of the present invention may be used. The contents of which are incorporated herein by reference.

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

When the color-curable composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably from 1 to 15 mass%, more preferably from 2 to 12 mass%, and most preferably from 3 to 10 mass%, based on the total solid content of the color- More preferably,% by mass. The color-curable composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<< Pigment Derivatives >>

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 with an acidic group, a basic group or a phthalimide methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoints of the dispersibility and the dispersion stability of the colorant A. Particularly preferably, it is a pigment derivative having a basic group. The combination of the resin (dispersant) and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, and the like.

The acidic group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a salt thereof, more preferably a carboxylic acid group or a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

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

<< Photopolymerization initiator >>

The colored curable 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 preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

More preferably, the compound is a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound or an acetophenone compound , At least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is particularly preferable.

Particularly, when the colored curable composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is important to form a fine pattern in a sharp shape, so that it is cured and developed without residue on the unexposed portion . From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for curing exposure, but this exposure device is sometimes damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging element. Further, by using an oxime compound, it is possible to further improve the dyeing property.

As specific examples of the photopolymerization initiator, reference can be made, for example, to paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

Examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, Irgacure-500, Irgacure-1959, Irgacure-127 (trade name: BASF) Ltd.) can be used.

As the aminoacetophenone-based initiator, commercially available Irgacure-907, Irgacure-369, Irgacure-379 (trade name, all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used.

As the acylphosphine-based initiator, commercially available Irgacure-819 and DAROCURE-TPO (all trade names, manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound.

As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

Also, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. have.

As a commercial product, Irgacure-OXE01 (manufactured by BASF) and Irgacure-OXE02 (manufactured by BASF) are suitably used. In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Aches NCI-831 and Adeka Aches NCI-930 (Adeka Co.) Can also be used.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Unexamined Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 where nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule The compound described in U.S. Patent Publication No. 7556910, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Preferably, reference can be made, for example, to Japanese Patent Application Laid-Open No. 2013-29760, paragraphs 0274 to 0275, the contents of which are incorporated herein by reference.

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

[Chemical Formula 29]

In the general 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), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The substituent described above may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

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

(30)

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

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

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

When the color-curable composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, more preferably from 0.5 to 30% by mass relative to the total solid content of the color- Is 1 to 20% by mass. Within this range, more excellent sensitivity and pattern formability can be obtained.

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

<< Polymerization inhibitor >>

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

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- -t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine cerium salt.

When the colored curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass with respect to the mass of the colored curable composition.

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

<< Surfactant >>

To the colored curable composition of the present invention, various surfactants may be added in order to further improve the coating property. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

For example, by containing the fluorine-containing surfactant, the liquid property (particularly, fluidity) when prepared as a coating liquid is further improved. That is, in the case of forming a film using a colored curable composition containing a fluorine-based surfactant, the wettability of the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, do. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoint of uniformity of the thickness of the coating film and liquidity, and is also excellent in solubility in the colored curable composition.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, and SC-103, SC-104, SC-105, SC1068, SC- PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-89090.

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerine ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Lysine, Lysine, Lysine, Lysine, Lysine, Lysine, Lysine, Lysine, Lysine, Ltd.) and the like. It is also possible to use PIONIN D-6112-W manufactured by Takemoto Yushi Co., Ltd.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005 and W017 (manufactured by Yusoh Co., Ltd.) and the like.

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

When the color-curable composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the color-curable composition.

The colored curable composition of the present invention may contain only one kind of surfactant or two or more kinds of surfactant. When two or more kinds are included, the total amount is preferably in the above range.

<< Silane coupling agent >>

The colored curable composition of the present invention may contain a silane coupling agent.

As the silane coupling agent, a silane compound having at least two functional groups different in reactivity from each other is also preferable, and it is particularly preferable that the silane coupling agent has an amino group and an alkoxy group as a functional group. Examples of such a silane coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name: KBM-602 manufactured by Shin-Etsu Chemical Co., -Aminopropyl-trimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name: KBE-602 ),? -aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.),? -aminopropyltriethoxysilane (trade name KBE-903 manufactured by Shin- And methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.). For details of the silane coupling agent, refer to paragraphs 0155 to 0158 of Japanese Laid-Open Patent Publication No. 2013-254047, the content of which is incorporated herein by reference.

When the colored curable composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the colored curable composition , And particularly preferably 0.1% by mass to 5% by mass.

The colored curable composition of the present invention may contain only one kind of silane coupling agent or two or more kinds of silane coupling agents. When two or more kinds are included, the total amount is preferably in the above range.

<< Other additives >>

Various additives, for example fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like, may be added to the color-curable composition of the present invention, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116, the contents of which are incorporated herein by reference.

The color-curable composition of the present invention may contain a sensitizer, a light stabilizer, and a thermal polymerization inhibitor described in paragraph &lt; RTI ID = 0.0 &gt; 0081 &lt; / RTI &gt; of the publication of Japanese Patent Application Laid-Open No. 2004-295116.

&Lt; Preparation method of colored curable composition >

The colored curable composition of the present invention is prepared by mixing the above-mentioned components.

Upon preparation of the colored curable composition, each component constituting the colored curable composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended continuously. In addition, the order of application and the working conditions at the time of compounding are not particularly limited. For example, the coloring curable composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions and dispersions, and they may be mixed It may be prepared as a composition.

The colored curable composition of the present invention is preferably filtered with a filter for the purpose of eliminating foreign matters or reducing defects. The filter can be used without particular limitation as far as it is conventionally used for filtration applications and 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) And the like). Of these materials, polypropylene (including high-density polypropylene) is preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 3.0 mu m, more preferably about 0.05 to 0.5 mu m. This range makes it possible to reliably remove fine foreign matter which inhibits the preparation of a uniformly colored and smooth colored curable composition in a subsequent step.

When using a filter, other filters may be combined. At this time, the filtering in the first filter may be performed once, or may be performed two or more times.

The first filter having different pore diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be formed of the same material as the first filter described above.

For example, the filtering in the first filter may be performed only with the dispersion, the other components may be mixed, and then the second filtering may be performed.

The colored curable composition of the present invention is suitably used for forming a colored layer of a color filter because it can form a cured film having excellent light resistance, flame retardancy and flatness. The colored curable composition of the present invention can be used for a solid-state image pickup device such as a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), or a color filter used for an image display device such as a liquid crystal display For example. In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, it can be suitably used for the production of color filters for solid-state image pickup devices such as CCD and CMOS.

<Color Filter, Pattern Forming Method, and Color Filter Manufacturing Method>

Next, the pattern forming method will be described in detail with reference to its manufacturing method. The color filter will be described in detail through its manufacturing method. A method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

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

In the pattern forming method of the present invention, a colored curable composition layer is formed on a support using the colored curable composition of the present invention, and unnecessary portions are removed to form a colored pattern.

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

In the pattern forming method of the present invention, the pattern formation may be performed by the so-called photolithography method, or the pattern formation may be performed by the dry etching method.

That is, the first aspect of the method for producing a color filter of the present invention comprises the steps of forming a colored curable composition layer on a support using the colored curable composition of the present invention, a step of exposing the colored curable composition layer to a pattern shape , And removing the unexposed portions to form a colored pattern. If necessary, a step of baking the colored curable composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided.

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

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

&Lt; Process of forming a colored curable composition layer &gt;

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

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

The coloring pattern in the present invention may be formed on the solid-state imaging element formation surface side (surface) of the substrate for a solid-state imaging element, or on the solid-state imaging element formation surface side (back surface).

On the support, if necessary, an undercoat layer may be provided for improving adhesion with the upper layer, preventing diffusion of the substance, or planarizing the surface of the substrate.

As the application method of the colored curable composition of the present invention on the support, various methods such as slit coating, inkjet coating, spin coating, pour coating, roll coating, screen printing and the like can be used.

Drying (prebaking) of the colored curable composition layer applied on the support can be carried out at a temperature of 50 to 140 캜 for 10 to 300 seconds in a hot plate, an oven or the like.

<< Exposure Process >>

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

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) of, for example 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² is most preferred.

The film thickness of the cured film is preferably 1.0 占 퐉 or less, more preferably 0.1 to 0.9 占 퐉, and still more preferably 0.2 to 0.8 占 퐉. When the film thickness is 1.0 占 퐉 or less, high resolution and high adhesion are likely to be obtained.

<< Pattern formation process >>

Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development of the unexposed portion can be removed by using a developing solution. As a result, the colored curable composition layer of the unexposed portion in the exposure process is eluted into the developer, leaving only the portion that is photo-cured.

As the developer, an organic alkali developing solution which does not cause damage to the underlying solid-state imaging element or circuit is preferable.

The temperature of the developing solution is preferably 20 to 30 占 폚, for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removing ability, the step of removing the developing solution every 60 seconds and newly supplying the developing solution may be repeated several times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene and the like. An alkaline aqueous solution diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, of these alkaline agents is preferably used as the developer.

An inorganic alkali may be used for the developer. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate and the like are preferable.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with purified water after development.

After the development, it is preferable to conduct the heat treatment (post-baking) after drying. If a multicolor colored pattern is formed, a cured film can be produced by sequentially repeating the steps for each color. As a result, a color filter is obtained.

Post baking is a post-development heat treatment for making the curing to be complete, and the heating temperature is preferably, for example, 100 to 240 占 폚, more preferably 200 to 240 占 폚.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so as to satisfy the above conditions.

The color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD and a CMOS, and is particularly suitable for a high-resolution CCD or CMOS exceeding 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 of each pixel constituting a CCD or CMOS and a microlens for condensing.

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.7 占 퐉 or less. The lower limit may be, for example, 0.1 占 퐉 or more, and may be 0.2 占 퐉 or more.

The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less. The lower limit may be, for example, 0.1 占 퐉 or more, and may be 0.2 占 퐉 or more.

In the case of forming a pattern by dry etching, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2013-64993, the contents of which are incorporated herein by reference.

<Solid-state image sensor>

The solid-state image pickup 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 the color filter of the present invention and functions as a solid-state imaging device.

The solid-state image pickup element has a plurality of photodiodes constituting a light receiving area of a solid-state image pickup device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like on a support, A device shielding film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the photodiode light-receiving portion, the device having a light-shielding film made of tungsten or the like, For example.

Further, it may be a structure having a condensing means (for example, a microlens or the like hereinafter) on the device protective film and below the color filter (near the support), or a structure having condensing means on the color filter.

<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. And is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with good display characteristics and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as IPS (In Plane Switching) or a pixel division system such as MVA (Multi-domain Vertical Alignment) (Twisted Nematic), VA (Vertical Alignment), O-CS (on-chip spacer), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend).

In addition, the color filter in the present invention can be used in a color-filter on array (COA) method which is bright and high definition. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA-type 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 in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. As for these members, for example, "Market of liquid crystal display peripheral materials, Chemicals (market issued by Shimada Kentaro Co., Ltd. in 1994)", "2003 Present condition and future prospect of liquid crystal related market (Issued by Fuji Chimera Soken Co., Ltd., 2003).

Concerning the backlight, the SID meeting digest 1380 (2005) (Konno et al.), Monthly Display December 2005, pages 18-24 (Yoshihiro Shimaya), 25-30 pages (Yagi Takaaki).

When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube. However, a red, green, and blue light emitting diode (LED) It is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, "part" and "%" are based on mass.

&Lt; Measurement of weight average molecular weight and number average molecular weight >

The weight average molecular weight and the number average molecular weight were measured by the following methods.

Types of columns: TSK Gel Super AW4000, TSK Gel Super AW3000, TSK Gel Super AW2500, TSK Gel Super AW2500

Developing solvent: N-methylpyrrolidone (containing 10 mmol / L LiBr)

Column temperature: 50 ° C

Flow rate (sample injection amount): 20 μL

Flow rate: 0.25 ml / min

Device name: HLC-8220 manufactured by Tosoh Corporation

GPC calibration curve base resin: polystyrene

&Lt; Measurement method of acid value >

The measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (mass ratio) and the obtained solution was stirred at 25 占 폚 using a potentiometric titration apparatus (trade name: AT-510, manufactured by Kyoto Denshi Kogyo) / L sodium hydroxide aqueous solution. Using the inflection point of the appropriate pH curve as an appropriate end point, the acid value was calculated by the following formula.

A = 56.11 x Vs x 0.1 x f / w

A: acid value (mgKOH / g)

Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)

f: Potency of 0.1 mol / L aqueous solution of sodium hydroxide

w: mass of the sample to be measured (g) (in terms of solid content)

<Measurement method of amine value>

The measurement sample was dissolved in acetic acid, and the resulting solution was subjected to neutralization titration with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometric titration apparatus (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). Using the inflection point of the appropriate pH curve as an appropriate end point, the amine value was calculated by the following formula.

B = 56.11 x Vs x 0.1 x f / w

B: Amine value (mgKOH / g)

Vs: Amount of 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL)

f: 0.1 mol / L Potency of perchloric acid / acetic acid solution

w: mass of the sample to be measured (g) (in terms of solid content)

(Synthesis Example)

(31)

&Lt; Synthesis Example of Colorant A-1 >

50 parts of DCSF (Zukai Kasei Kasei), 74.76 parts of 2,6-dimethyl aniline, 27.58 parts of zinc chloride, and 200 parts of sulfolane were placed in a flask and stirred at 200 ° C for 4 hours. Thereafter, the obtained reaction solution was cooled to room temperature and added dropwise with 500 parts of 2 mol / L hydrochloric acid. The precipitated crystals were separated by filtration. The crystals were dispersed and washed with 300 parts of acetonitrile at 40 ° C., filtered and air-dried for 10 hours to obtain 46.5 parts (yield: 65.6%) of the colorant A-1.

<Synthesis of intermediate 1>

20 parts of the colorant A-1 and 106 parts of phosphorus oxychloride were placed in a flask, which was stirred for 2 hours at 60 deg. The obtained reaction solution was cooled to room temperature, and the reaction solution was dropped into 1500 parts of ice water and stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts of water, and blow-dried for 10 hours to obtain 18.5 parts (yield: 89.4%) of intermediate 1.

<Synthesis of Colorant A-4>

7 parts of Intermediate 1 and 2.05 parts of benzenesulfonamide were dissolved in 40 parts of chloroform to prepare diazabicyclo-undecene (1,8-diazabicyclo [5.4.0] undec-7-ene ene) (2.32 parts) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Thereafter, 100 parts of water was added to the obtained reaction solution, which was then washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified by column chromatography, and concentrated under reduced pressure to obtain 3 parts (yield: 34%) of colorant A-4.

&Lt; Synthesis Example of Colorant A-2 >

Colorant A-2 was synthesized by changing 2,6-dimethyl aniline used in the synthesis of colorant A-1 to 2,6-diethylaniline.

<Synthesis Example of Colorant A-3>

Colorant A-3 was synthesized by changing 2,6-dimethyl aniline used in the synthesis of colorant A-1 to 2,6-diisopropylaniline.

<Synthesis Example of Colorant A-5>

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

&Lt; Synthesis Example of Colorant A-6 >

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

&Lt; Synthesis Example of Colorant A-7 >

Colorant A-7 was synthesized by changing 2,6-dimethyl aniline used in the synthesis of colorant A-1 to 2,4,6-trimethylaniline.

&Lt; Synthesis Example of Colorant A-8 >

(32)

50 parts of DCSF (available from Kukai Kasei Kasei), 52.5 parts of 2,6-diisopropylaniline and 200 parts of sulfolane were placed in a flask and stirred at an outer temperature of 80 ° C for 4 hours. Thereafter, the obtained reaction solution was cooled to room temperature and added dropwise with 500 parts of 2 mol / L hydrochloric acid. The precipitated crystals were separated by filtration. The crystals were dispersed washed with 300 parts of acetonitrile at 40 degrees, filtered and air-dried for 10 hours to obtain 28 parts (yield: 45%) of intermediate 2.

25 parts of the intermediate 2, 14.4 parts of 2,6-dimethyl aniline, 11.1 parts of zinc chloride and 100 parts of sulfolane were added, and the mixture was stirred at an external temperature of 200 ° C for 4 hours. Thereafter, the obtained reaction solution was cooled to room temperature, and 200 parts of 2 mol / L hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration. The crystals were dispersed and washed with 120 parts of acetonitrile at 40 ° C., filtered and air-dried for 10 hours to obtain 25.1 parts (yield: 86%) of the colorant A-8.

<Synthesis Example of Colorant A-9>

Colorant A-9 was synthesized by changing 2,6-dimethyl aniline used for the synthesis of colorant A-1 to N- (3-amino-2,4,6-trimethylphenyl) acetamide.

&Lt; Synthesis Example of Colorant A-10 >

Colorant A-10 was synthesized by changing 2,6-dimethyl aniline used in the synthesis of colorant A-1 to 2-methylaniline.

(33)

&Lt; Evaluation of solvent solubility of colorant &

0.1 g of the coloring agent was added to the sample tube, and 10 ml of the organic solvent shown in the following Table 1 was introduced by using a hole pipette, and the stopper was closed and treated with ultrasonic waves for 3 minutes. The resulting solution was stored in a water bath (Bath) at 23 DEG C for 60 minutes. 5 ml of this supernatant was filtered with a PTFE membrane filter having a pore diameter of 5 m and further filtered with a PTFE membrane filter having a pore diameter of 0.25 m to remove insolubles.

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

[Table 1]

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

<Preparation of Dispersion Using (A) Colorant>

(A), a dispersant (B), a pigment derivative (C), a dye (D) and a solvent were mixed in the proportions shown in Table 2 below, and uniformly stirred and mixed. Thereafter, zirconia beads And dispersed by means of a beads mill for 5 hours to prepare a dispersion.

[Table 2]

The compounds shown in the table are as follows.

(A) Colorant

A-1 to A-10: Colorants A-1 to A-10

R-1 to R-5: Comparative compounds (the following structures)

(34)

(B) Dispersant

[Table 3]

(35)

(C) Pigment derivatives

C-1: Structure

(36)

(H) Dye

H-1 to H-3:

(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.

, 13.0 parts (blue pigment, average particle diameter 55 nm) of CI Pigment Blue 15: 6 (hereinafter also referred to as "PB 15: 6"), 5.0 parts of a disperser Daisper byk111, Were mixed and dispersed for 3 hours by means of a bead mill (zirconia beads having a diameter of 0.3 mm). This dispersion was then subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm &lt; ³ &gt; using NANO-3000-10 (manufactured by Nippon Bionics Co., I did. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion, pigment concentration 13%) used for the color-curing composition of Example or Comparative Example.

The average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.) with respect to the obtained blue pigment dispersion P1, and was found to be 24 nm.

<Preparation of blue pigment dispersion P2>

19.5 parts by mass of PB 15: 6 (average particle diameter: 55 nm), 2.95 parts by mass of BYK-161 (manufactured by BYK) as a dispersant, and 20 parts by mass of alkali soluble resin 1 (copolymer of benzyl methacrylate / methacrylic acid, 30% (Solution 9.93 parts by mass) and 165.3 parts by mass of PGMEA were mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm in diameter) for 3 hours. This mixed solution was then subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser Nano-3000-10 (manufactured by Nippon Bionics Co., Ltd.) This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion P2. The average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrack NanoTrack UPA-EX150 (Nikkiso Co., Ltd.)) relative to the obtained blue pigment dispersion P2.

&Lt; Preparation of blue pigment dispersion P3 >

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

(38)

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

&Lt; Preparation of blue pigment dispersion P4 >

A pigment dispersion P4 was prepared in the same manner as in the preparation of the blue pigment dispersion P2 except that the following dispersant D2 was used as the dispersant.

[Chemical Formula 39]

The acid value of dispersant D2 was 100 mg KOH / g. The weight average molecular weight of dispersant D2 was 20,000. 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

The following components were mixed, dispersed and dissolved to obtain colored and curable compositions of Examples and Comparative Examples.

(A) Dispersion Using Colorant (Dispersion PA1 to PA46): 0.31 part

Solvent (PGMEA, cyclohexanone or cyclopentanone): 0.863 part

Alkali-soluble resin (compound of the following J1 or J2): 0.03 part

Dispersant (Sol Spurs 20000: (1% cyclohexane solution, manufactured by Nippon Rubrizol Co., Ltd.)): 0.125 parts

Photopolymerization initiator (compound of the following C-5 or C-9): 0.012 part

Blue Pigment Dispersion (Blue Pigment Dispersion P1 to P4) (Pigment Concentration 13%): 0.615 parts

Curing compound: 0.07 part

Surfactant (glycerol propoxide: (1% cyclohexane solution)): 0.048 part

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

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

<Evaluation>

<< Evaluation of spectroscopic before and after development >>

CT-4000L solution (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD. Made by Transparent Materials Co., Ltd.) was coated on a glass wafer so that the dry film thickness was 0.1 mu m and dried to form a transparent film. Heat treatment was carried out.

The colored curable composition was coated on a glass wafer having a transparent film formed thereon using a spin coater so as to have a dry film thickness of 0.6 占 퐉 and subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 占 폚. Subsequently, exposure was performed at an exposure dose of 500 mJ / cm ² at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Thus, a color filter was obtained.

The color filter thus obtained was measured for its transmittance in a wavelength range of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of ultraviolet-visible near infrared spectrophotometer UV3600 (Shimadzu Corporation).

The color filter after the measurement of the transmittance was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS CO., LTD.), And using CD-2000 (manufactured by FUJIFILM ELECTRONICS MATERIALS CO. And puddled at 23 DEG C for 60 seconds. Subsequently, the color filter was rotated by a rotating device at a rotational speed of 50 rpm, pure water was supplied from a spray nozzle through a spray nozzle from above the rotation center to a rinse treatment, and spray-dried. After drying the color filter, the transmittance was measured again. The values of the transmittance fluctuation before and after development (the transmittance before development is T0 and the transmittance after development is T1) are evaluated based on the following criteria.

A: Good When the maximum fluctuation value of the transmittance before and after development in the entire region of 300 nm to 800 nm is less than 2%

B: slightly better In the entire region of 300 nm to 800 nm, the maximum fluctuation value of the transmittance before and after development is 2% or more and less than 5%

C: the maximum fluctuation value of the transmittance before and after the development in the entire region of 300 nm to 800 nm sufficiently is not less than 5% and less than 10%

D: insufficient maximum fluctuation value of the transmittance before and after development in the entire region of 300 nm to 800 nm is not less than 10%

<< Heat resistance evaluation >>

The color filter (? E * ab value) before and after heating was measured with a color meter MCPD-1000 (manufactured by OTSUKA DENKI CO., LTD.) On the color filter obtained above and the heat resistance was evaluated according to the following criteria. The color filter was placed on a hot plate at 200 캜 so as to be in contact with the wafer surface, and heated for 1 hour. The value of? E * ab indicates that the smaller the value, the better the heat resistance. The value of? E * ab is a value obtained from the following color difference formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (Japanese Society for Color Science Handbook of Color Science Handbook ). ? E * ab = {(? L *) 2+ (? A *) 2+ (? B *) 2} 1/2.

A: value of? E * ab is 0 or more and less than 1.0

B: value of? E * ab is 1.0 or more and less than 2.0

C: value of? E * ab is 2.0 or more and less than 3.0

D: value of DELTA E * ab is 3.0 or more

<< Light fastness evaluation >>

A quartz inner filter, a 275 nm cut outer filter, an illuminance of 75 mw / m ² (300 to 400 nm), and a black panel temperature of 63 캜 were measured for the color filter obtained above using a light resistance tester (Suga Shikenki SX- And a light resistance test was conducted for 10 hours under the conditions of a humidity of 50%.

The color difference (? E * ab) before and after the light resistance test was measured by a spectrophotometer MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.). Based on the measured color difference (? E * ab), the light resistance was evaluated according to the following evaluation criteria. The smaller this value is, the better the light resistance is.

A: value of? E * ab is 0 or more and less than 1.0

B: value of? E * ab is 1.0 or more and less than 2.0

C: value of? E * ab is 2.0 or more and less than 3.0

D: value of DELTA E * ab is 3.0 or more

<< Evaluation of dispersion stability >>

(Unit: mPa 占 퐏) immediately after dispersion and viscosity after being left at 45 占 폚 for 3 days after dispersion using an E-type viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.) ? 2 (unit: mPa 占 퐏) was measured at room temperature to calculate the increase ratio (? 2 -? 1) /? 1 × 100. Based on the calculated increase rate, the dispersion stability was evaluated according to the following evaluation criteria.

The smaller the percentage increase, the better the dispersion stability.

Were evaluated according to the following criteria.

A: Increase of 10% or less

B: Increase of 10% or more and 20% or less

C: Increase rate is greater than 20%

[Table 4]

[Table 5]

As shown in Tables 4 and 5, in Examples, the spectral fluctuation before and after development was small, and a film excellent in light resistance was able to be formed. Further, heat resistance was also excellent. In addition, the color-curing composition of the examples was excellent in dispersion stability.

On the other hand, in the comparative example, the spectral fluctuation before and after development could not be compatible with the light resistance.

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

Alkali-soluble resin: The following structure

(40)

Photopolymerization initiator:

(41)

Curable compound

KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Shin Nakamura Kagaku)

NK Ester A-DPH-12E (manufactured by Shin Nakamura Kagaku Co., Ltd.)

KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)

Polyfunctional thiol compound (chain transfer agent): The following structure

(42)

Epoxy compound

E-1: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.

E-3: Epiclon N660 (manufactured by DIC Corporation)

Claims (30)

1. A colorant comprising a colorant A having a structure represented by the following formula (1), a curable compound, and an organic solvent,
A coloring curable composition wherein the coloring agent A is dispersed in the organic solvent;
[Chemical Formula 1]

In formula (1), R ¹ , R ⁵ , R ⁶ and R ¹⁰ each independently represents a hydrogen atom or an alkyl group, and at least one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ represents an alkyl group ,
R ² , R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom,
R ¹¹ represents a sulfonate group. delete delete delete The method according to claim 1,
R ¹ , R ⁵ , R ⁶ and R ¹⁰ are each independently an alkyl group. The method according to claim 1,
R ¹ , R ⁵ , R ⁶ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. The method according to claim 1,
R ¹ , R ⁵ , R ^6, and R ¹⁰ are each independently a methyl group, an ethyl group, a propyl group, or an isopropyl group. delete 1. A colorant comprising a colorant A having a structure represented by the following formula (1), a curable compound, and an organic solvent,
A coloring curable composition wherein the coloring agent A is dispersed in the organic solvent;
(2)

Formula (1) of, R ¹ ~ R ¹⁰ are, each independently, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ^{X1, X1} -SR, -COR ^{X1, X1} -COOR, -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 bis (sulfonyl) imide group. The method according to claim 1,
Further comprising a pigment having a phthalocyanine skeleton. The method of claim 10,
Wherein the pigment having the phthalocyanine backbone is CI Pigment Blue 15: 6. The method of claim 11,
Wherein the content of the CI Pigment Blue 15: 6 is 100 to 200 parts by mass relative to 100 parts by mass of the colorant A. delete The method according to claim 1,
Wherein at least one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a branched alkyl group. The method according to claim 1,
R ¹ , R ⁵ , R ^6, and R ¹⁰ are each independently a branched alkyl group. The method according to any one of claims 1, 5 to 7, 9 to 12, and 14 to 15,
Wherein the organic solvent is at least one selected from an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent. The method according to any one of claims 1, 5 to 7, 9 to 12, and 14 to 15,
And a photopolymerization initiator, wherein the curable compound is a radically polymerizable compound. The method according to any one of claims 1, 5 to 7, 9 to 12, and 14 to 15,
Further comprising an acidic dispersant having an acid value of 30 mgKOH / g or more. 19. The method of claim 18,
Wherein the coloring and curing composition comprises two or more kinds of the acidic dispersing agent. delete The method according to any one of claims 1, 5 to 7, 9 to 12, and 14 to 15,
As a coloring agent other than the coloring agent A, further comprises a dye. 23. The method of claim 21,
Wherein the dye is a dye having a skeleton selected from phthalocyanine, triarylmethane and pyromethene. The method according to any one of claims 1, 5 to 7, 9 to 12, and 14 to 15,
Coloring curable composition for a color filter. A color filter comprising the color-curable composition according to any one of Claims 1 to 7, 9 to 12, and 14 to 15. A step of forming a colored curable composition layer on a support using the color-curable composition according to any one of claims 1 to 7, 9 to 12, and 14 to 15,
A step of exposing the colored curable composition layer in a pattern shape,
And removing the unexposed portion by development to form a colored pattern. A method of manufacturing a color filter, comprising the pattern forming method according to claim 25. A solid-state imaging device having the color filter according to claim 24. An image display apparatus having the color filter according to claim 24.
The method according to claim 1,
R ¹ , R ⁵ , R ⁶ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms. The method according to claim 1,
And R ¹ , R ⁵ , R ⁶ and R ¹⁰ are isopropyl groups.