JP2009075482A - Curable composition, color filter, method for producing color filter, and solid-state imaging device - Google Patents

Abstract

[PROBLEMS] To provide a curable composition having excellent storage stability and good developability, and, even when a pigment is contained, has excellent dispersibility and dispersion stability of the pigment, and has good developability and pattern formation. The present invention provides a curable composition having excellent properties, a color filter having a colored region formed thereby, a method for producing the same, and a solid-state imaging device including the color filter.
(A) A resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated double bond. And a curable composition containing (D) a solvent. Furthermore, it becomes a colored curable composition for color filter formation by containing (E) pigment as a coloring agent.
[Selection figure] None

Description

  The present invention relates to a curable composition suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a colored region formed by the curable composition. And a method for manufacturing the same.

  The color filter is an essential component for liquid crystal displays and solid-state image sensors. The color filter is prepared using a curable composition containing a colorant (pigment or dye). When the colorant is a pigment, it is necessary to add a dispersant (for example, see Patent Document 1) in order to ensure dispersibility and dispersion stability.

  In recent years, solid-state imaging devices have been required to reduce pixel size (pattern width and film thickness) as the number of pixels increases. Accordingly, it is necessary to increase the pigment concentration in the curable composition. However, it has been found that when the pigment concentration is increased, the content of the dispersion resin / alkali-soluble resin in the curable composition is inevitably lowered, so that the dispersibility / dispersion stability deteriorates. In order to improve dispersibility and dispersion stability, it has been proposed to increase the amount of a specific dispersant added (for example, see Patent Document 1). However, there has been a problem that developability is lowered by increasing the amount of the dispersant added.

In addition, liquid crystal displays for TV use are required to have higher image quality than those of conventional monitor uses, and are required to improve contrast and color purity.
With respect to curable compositions for color filter production, attempts have been made to improve contrast by using finer particle sizes of pigments to be used (see, for example, Patent Document 2).
However, when the particle size of the pigment is reduced, the surface area of the pigment increases, which causes a problem of deterioration in storage stability. If the amount of the dispersant added is increased in order to ensure storage stability, as in the case of the solid-state imaging device, the developability deteriorates, and there is a problem that it is difficult to form a good pattern.

That is, in recent years, color filters with high contrast and good color characteristics that are compatible with highly functional solid-state imaging devices and liquid crystal displays are difficult to manufacture with conventional curable compositions containing dispersants, and are stable in dispersion. Therefore, a curable composition that can achieve both compatibility and developability has been desired.
JP-A-9-176511 JP 2006-30541 A

An object of the present invention is to provide a curable composition having excellent storage stability and good developability. Furthermore, even if it contains a pigment, it is providing the curable composition which was excellent in the dispersibility and dispersion stability of a pigment, was excellent in developability, and was excellent in pattern formation property.
A further object of the present invention is to provide a color filter having a color pattern having a high resolution and good color characteristics formed from a colored curable composition having good dispersion stability and developability of the pigment, and a production method excellent in productivity thereof. Is to provide.
Another object of the present invention is to provide a solid-state imaging device including a color filter having a coloring pattern with high resolution and good color characteristics.

In view of the above circumstances, the present inventors have conducted intensive research and found that the above problems can be solved by using a resin having a specific structure, and have completed the present invention.
That is, the object of the present invention is achieved by the following means.
<1> (A) Resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group, (B) a photopolymerization initiator, (C) an ethylenically unsaturated double bond The curable composition containing the compound to contain and the (D) solvent.
<2> The curable composition according to <1>, further comprising (E) a pigment.

<3> (A) a pigment dispersion prepared by including a resin having a main chain portion containing a nitrogen atom and a side chain portion having an oxyalkylene group, and (E) a pigment; and (B) The curable composition according to <2>, which is obtained by mixing a photopolymerization initiator, (C) a compound containing an ethylenically unsaturated double bond, and (D) a solvent.
<4> The curable composition according to any one of <1> to <3>, further comprising (F) an alkali-soluble resin.
<5> The curable composition according to any one of <1> to <4>, wherein the main chain portion including the nitrogen atom includes a polyamine structure.

<6> A color filter having a colored region formed of the curable composition according to any one of <2> to <5> on a support.
<7> A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition according to any one of <2> to <5> on the support; A method for producing a color filter, comprising: an exposure step of pattern exposure of a colored layer through a mask; and a development step of developing the colored layer after exposure to form a colored pattern.
<8> A solid-state imaging device comprising a color filter obtained by the method for producing a color filter according to <7>.

The curable composition of the present invention has a main chain portion having a nitrogen atom and an oxyalkylene that is hydrophilic and has excellent solubility in organic solvents such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. Since a resin having a side chain structure containing a group is used, stability improvement can be achieved without impairing developability, thereby achieving both dispersibility / dispersion stability and developability, which has been difficult in the past. I was able to. That is, by having an oxyalkylene group excellent in solubility in an organic solvent in the side chain, excellent stability is achieved due to the effect of suppressing solid precipitation over time. The effect is particularly remarkable when a pigment is used as a colorant. For this reason, the colored area | region formed with the curable composition of this invention and the colored curable composition containing a pigment becomes a thing with high resolution and high color purity. Further, by using such a colored curable composition, it is possible to obtain a high-contrast color filter with a resolution, a solid-state imaging device including the color filter, a liquid crystal display with a high contrast ratio, and the like.
The colored region in the present invention includes a colored pixel (colored pattern) region and a light shielding film forming region in the color filter.

According to the present invention, a curable composition having excellent storage stability and good developability can be provided, and even when a pigment is contained, the pigment has excellent dispersibility and dispersion stability, and A curable composition having good developability and excellent pattern forming property can be provided.
In addition, according to the present invention, it is possible to provide a color filter having a colored pattern with high resolution and good color characteristics, a manufacturing method excellent in productivity thereof, and a solid-state imaging device including the color filter. .

  Hereinafter, the best mode for carrying out the invention will be described in detail. In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution means that what has a substituent is included with what does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The curable composition of the present invention includes (A) a resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group, (B) a photopolymerization initiator, and (C) an ethylenic resin. It contains a compound containing an unsaturated double bond and (D) a solvent, and further contains (E) a pigment depending on the use of the curable composition.
Hereinafter, each component contained in the curable composition of this invention is demonstrated one by one. First, (A) a resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group (hereinafter referred to as a specific resin as appropriate), which is an important requirement of the present invention, will be described.

<(A) Resin having a main chain portion containing a nitrogen atom and a side chain portion containing an oxyalkylene group>
The specific resin (A) according to the present invention is a resin having (i) a main chain portion containing a nitrogen atom and (ii) a side chain portion containing an oxyalkylene group, and has a function of improving developability. At the same time, it is excellent in the effect of suppressing solid matter precipitation over time and can achieve excellent storage stability. Furthermore, when a pigment is included as a colorant in the system, it also functions as a dispersant that enhances dispersibility and dispersion stability.

  (I) The main chain portion containing a nitrogen atom refers to a chain structure containing a nitrogen-containing functional group as a repeating unit, and more specifically, in the range of a number average molecular weight of 200 to 50,000. A certain oligomer chain or polymer chain. As for the number average molecular weight of the principal chain part comprised including a nitrogen atom, 300-20,000 are more preferable, and 500-10,000 are the most preferable. When the number average molecular weight of the (A) specific resin of the present invention is in the above range, the curable composition has excellent dispersibility and developability. The number average molecular weight of the resin can be measured by measuring the increase in boiling point, viscosity, ratio of terminal functional group and repeating unit by NMR, or by a method such as gel permeation chromatography.

  The main chain portion containing a nitrogen atom in the specific resin (A) of the present invention preferably contains a polyamine structure. In addition, the nitrogen-containing functional group contained in the main chain portion is preferably a functional group represented by the following general formula (I-1) or general formula (I-2).

In general formulas (I-1) and (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, or cycloalkyl. Represents a group, an aryl group, an acyl group or an alkoxycarbonyl group. l, m, and n each independently represent an integer of 1 to 10.
A represents a partial structure containing a nitrogen atom represented by the following general formula (I-3), general formula (I-4), general formula (I-5), or general formula (I-6).

In general formula (I-3), general formula (I-4), general formula (I-5) and general formula (I-6), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are respectively Independently, it represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, or represents a linking site with a side chain described later. That is, at least one of R ^{8 to} R ¹² serves as a single bond or a divalent linking group, which serves as a site for connecting side chain portions described later. The side chain structure connected here will be described in detail below.
When A in general formula (I-2) is represented, one end of the structure represented by general formula (I-3) to general formula (I-6) is linked to-(CR ⁶ R ⁷ ) n-. The other terminal has a terminal group selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, or serves as a linking site with a side chain described later.

As the alkyl group in the case where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ^{7 in the} general formula (I-1) and the general formula (I-2) represent an alkyl group, The alkyl group having 1 to 30 carbon atoms is preferable, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-octyl and the like.

The cycloalkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in the general formula (I-1) and the general formula (I-2) has a carbon number. 3-30 alkyl groups are preferred, and examples include cyclopentyl, cyclohexyl, cyclooctyl and the like.

The acyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in the general formula (I-1) and the general formula (I-2) has 1 carbon atom. ˜30 acyl groups are preferred, and examples include formyl, acetyl, benzoyl and the like.

The alkoxycarbonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in the general formula (I-1) and the general formula (I-2) 1-30 alkyl groups are preferable, and methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, etc. are mentioned.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ^{7 in the} general formula (I-1) and the general formula (I-2) include a hydrogen atom, an alkyl group, and a fluorine atom. Or it is preferable that it is a chlorine atom, and it is most preferable that it is a hydrogen atom.
l, m, and n are integers of 1 to 10, preferably 1 to 5, and most preferably 1 is 2, and m and n are all 1.

  A is preferably a structure represented by General Formula (I-3) or General Formula (1-4), and most preferably General Formula (I-3).

In the general formula (I-3) to general formula (I-6), when R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group, an alkyl group, a cycloalkyl group, an acyl group, and Examples of the alkoxycarbonyl group include the same groups as those described for R ^{1 to} R ⁷ in the general formula (I-1) and the general formula (I-2).
R ⁸ , R ⁹ , R ¹⁰ , R ^11, and R ¹² preferably represent a hydrogen atom, an alkyl group, or a linkage site with a side chain, and more preferably represent a linkage site with a hydrogen atom or a side chain.

The main chain portion containing a nitrogen atom contains a nitrogen atom in addition to the nitrogen atom-containing functional group represented by the structural unit represented by the general formula (I-1) or the general formula (I-2). It may be configured to further have a structural unit not containing any divalent linking group or nitrogen atom.
(A) As a bivalent coupling group which can be introduce | transduced into the principal chain part of specific resin, a C1-C30 alkylene group (for example, a methylene, ethylene, propylene, etc.), a C3-C30 cycloalkylene group ( For example, 1,4-cyclohexylene and the like, an arylene group (for example, 1,4-phenylene and the like) and the like can be mentioned.
The polymerization molar ratio of the nitrogen-containing functional group and the divalent linking group (structural unit) not containing a nitrogen atom is preferably nitrogen-containing functional group: other linking group = 100: 0 to 1:99, 100: Most preferably, it is 0-30: 70.

  (A) specific resin of this invention has a side chain part which has ii) oxyalkylene group. Here, the oxyalkylene group is preferably a structure represented by the following general formula (II).

  In general formula (II), B represents an alkylene group having 1 to 10 carbon atoms. C represents a hydrogen atom or a monovalent organic group. p represents an integer of 1 to 5,000.

B is preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. The alkylene group represented by B may further have a substituent. Examples of the substituent that can be introduced include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, an alkoxy group, Examples include an acyl group and an alkoxycarbonyl group.
C is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group or an alkoxycarbonyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms. Group, an acyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or An alkoxycarbonyl group having 1 to 20 carbon atoms is most preferable.
By having such a side chain structure in the specific resin (A) of the present invention, developability is improved, and further, when a pigment is used in combination, the dispersion performance of the pigment is also improved. p is preferably 1 to 2,000, and most preferably 1 to 1,000.

  The graft chain-containing resin of the present invention may be a graft polymer having a side chain other than the side chain having the oxyalkylene portion, and has, for example, a polyester represented by the general formula (III) as a side chain structure. May be. By having a polyester structure in the side chain, the pigment dispersion performance is further improved.

  In general formula (III), D represents an alkylene group having 1 to 30 carbon atoms. E represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group. q represents an integer of 1 to 5,000.

  The hydrogen atom, alkyl group, cycloalkyl group, acyl group or alkoxycarbonyl group represented by E is the hydrogen atom, alkyl group, cycloalkyl group, acyl group or alkoxycarbonyl represented by C in the general formula (II). Synonymous with group.

D is preferably an alkylene group having 1 to 20 carbon atoms, and most preferably an alkylene group having 1 to 15 carbon atoms. E is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 1 to 20 carbon atoms, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Most preferred are ˜20 acyl groups.
q is preferably 1 to 2,000, and most preferably 1 to 1,000.

The molar ratio of the side chain part having an oxyalkylene group to the other side chain part is preferably such that the side chain part having an oxyalkylene part: the other side chain part = 100: 0 to 1:99, Most preferably, it is 0 to 30:70.
As the most preferable embodiment of the specific resin (A) in the present invention, a substituent having a main chain structure such as polyethyleneimine or polyallylamine and having an oxyalkylene structure selected from oxyethylene and oxypropylene in its side chain is provided. It is a polymer compound having a weight average molecular weight of about 3,000 to 50,000.

  A resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group which can be suitably used in the present invention is described in, for example, JP-A-56-57,747. According to the method, it can be produced by reacting an oligomer or polymer having a nitrogen atom with a cyclic ether in the presence of a catalyst.

As the catalyst used in the reaction, a basic compound is preferably used. For example, hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, etc.) Amine compounds (triethylamine, tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc.), alkyllithium (methyllithium, ethyllithium, n-butyllithium, tert-butyllithium, etc.) ), Grignard reagents (methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, etc.), etc. are preferred, with hydroxides being particularly preferred, and lithium hydroxide, sodium hydroxide or potassium hydroxide being most preferred.
Although there is no restriction | limiting in particular in the usage-amount of a catalyst, It is preferable to use 0.01 mol%-10 mol% with respect to the nitrogen atom mole number of the oligomer or polymer which has a nitrogen atom, 0.1 mol%-5 mol% Most preferably it is used.

  The cyclic ether used in this reaction is preferably a 3-membered or 4-membered cyclic ether, and ethylene oxide, propylene oxide and oxetane are preferred.

  The molar ratio between the cyclic ether used in this reaction and the total number of moles of nitrogen atoms contained in the oligomer or polymer having a nitrogen atom is cyclic ether: nitrogen atom of oligomer or polymer having nitrogen atom = 1: 3 to 1. : 10,000 is preferable, and 1:10 to 1: 5,000 is most preferable.

The reaction may be performed in the absence of a solvent or in the presence of a solvent.
When a solvent is used, examples of the solvent include aliphatic hydrocarbon solvents (eg, pentane, hexane, cyclohexane, etc.), aromatic hydrocarbon solvents (eg, toluene, xylene, mesitylene, etc.), sulfoxide solvents (eg, Dimethyl sulfoxide, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), ester solvents (eg, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol monomethyl ether acetate, etc.), ether solvents (Eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), nitrile solvents (eg, acetonitrile, propiononitrile, etc.), amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide) N- methylpyrrolidone) and halogenated solvents (e.g., chloroform, 1,2-dichloroethane and the like) can be used.
The reaction is preferably carried out without solvent from the viewpoint of productivity.

The reaction temperature is preferably 10 to 250 ° C, and most preferably 50 to 200 ° C.
The reaction time is preferably 1 to 48 hours, and most preferably 2 to 24 hours.

  Specific examples of the (A) specific resin used in the present invention are shown below together with the weight average molecular weight (Mw), but the present invention is not limited thereto. In addition, the numerical value written together in each structural unit represents a polymerization degree. The molecular weight is a value determined by the GPC method.

Although content of (A) specific resin in the curable composition of this invention is suitably selected according to the objective, it is the range of 0.1-20 mass% in conversion of solid content, and it is storage stability. From the viewpoint, it is preferably in the range of 1 to 10% by mass.
In particular, in the case of using a pigment containing pigment as a formation by the curable composition of the present invention, it is preferable to prepare a pigment dispersion in advance and then mix it with other components. Is preferably used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the pigment solid content.

<(B) Photopolymerization initiator>
The curable composition of this invention contains (B) photoinitiator for a sensitivity and pattern formation improvement. The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of a polymerizable component in the present invention, and preferably has an absorption in a wavelength region of 300 to 500 nm. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples thereof include a rubiimidazole compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, an acylphosphine (oxide) compound, and an alkylamino compound.
Hereinafter, each of these compounds will be described in detail.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

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

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

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

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

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

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

Examples of the azo compound include azo compounds described in JP-A-8-108621.
Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

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

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

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

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

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

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

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

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

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability and sensitivity. It is preferably substituted with. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

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

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

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

  As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a triazine compound, an alkylamino compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halo A compound selected from the group consisting of a methyloxadiazole compound and a 3-aryl-substituted coumarin compound is preferred.

  More preferably, they are triazine compounds, alkylamino compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds. More preferably, at least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds, and biimidazole compounds.

  In particular, when the curable composition of the present invention is used for the formation of colored pixels in a color filter of a solid-state image sensor, the pigment concentration of the curable composition is high due to the formulation, so the amount of initiator added is reduced and the sensitivity is increased. Will fall. Further, when exposure is performed with a stepper, if an initiator that generates a halogen-containing compound at the time of exposure, such as a triazine compound, is used, it causes corrosion of the equipment and is difficult to use. Considering these, as the photopolymerization initiator that satisfies the sensitivity and various performances, an oxime compound is preferable, and an oxime compound having absorption at 365 nm is most preferable.

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

<(C) Compound containing ethylenically unsaturated double bond>
The curable composition of the present invention contains a compound containing an ethylenically unsaturated double bond other than the resin (hereinafter, sometimes simply referred to as “compound containing an ethylenically unsaturated double bond”). can do.

  The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, other than the resin, and having a terminal ethylene Selected from compounds having at least one, preferably two or more, unsaturated unsaturated bonds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

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

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

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

  Furthermore, monomers containing acid groups can also be used, for example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. In these, pentaerythritol triacrylate succinic acid monoester etc. are mentioned.

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

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

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

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

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

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

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

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei), UA-7200 (Shin Nakamura Chemical Co., Ltd.) Product).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  The content of the compound containing (C) an ethylenically unsaturated double bond in the present invention is preferably 1% by mass to 90% by mass in the solid content of the curable composition of the present invention, and 5% by mass. % To 80% by mass is more preferable, and 10% to 70% by mass is even more preferable.

  In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the compound containing (C) an ethylenically unsaturated double bond is 5% by mass to 50% by mass within the above range. %, More preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

(D) Solvent The curable composition of the present invention has at least one (D) solvent. The (A) specific resin, (B) polymerization initiator, (C) the polymerizable compound and the (D) solvent are used, and when the (E) pigment described later is used, the curable composition in which the pigment is well dispersed. Product can be prepared.

Examples of the solvent (D) in the present invention include liquids selected from the organic solvents shown below, and the solubility of each component contained in the pigment dispersion and the applicability when applied to a curable composition. These are selected in consideration of the above and are not particularly limited as long as these desired physical properties are satisfied, but are preferably selected in consideration of safety.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

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

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

  As content of (D) solvent in the curable composition of this invention, 50-90 mass% is preferable, 60-95 mass% is more preferable, 70-90 mass% is the most preferable. When the content of the solvent is within the above range, it is advantageous in terms of suppressing the generation of foreign matter.

  The curable composition of this invention may further contain the component explained in full detail as needed.

<(E) Pigment>
The curable composition of the present invention may contain a pigment. By containing a pigment, it can be applied to formation of a colored region in a color filter, printing ink, and the like.

  As the pigment contained in the curable composition, conventionally known various inorganic pigments or organic pigments can be used, and high transmittance is preferable.

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

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

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

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37;
C. I. Pigment Black 1

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.
The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If the ratio is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm. If the ratio is 100: 51 or more, the main wavelength tends to be closer to the short wavelength, and the color resolution may not be improved. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the required spectrum.

As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
The mass ratio of the blue pigment and the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

When used for a color filter, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle diameter of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

  Among these, the pigment is preferably a pigment selected from anthraquinone, azomethine, benzylidene, cyanine, diketopyrrolopyrrole, and phthalocyanine.

  The content of the pigment in the curable composition of the present invention is preferably 30% by mass or more based on the total solid content of the curable composition, including the case where it is used for forming a color filter color pattern. It is more preferably 35% by mass or more, and most preferably 40% by mass or more and 80% by mass or less.

Next, other components that can be added to the curable composition of the present invention will be described.
<Alkali-soluble resin>
An alkali-soluble resin can be added to the curable composition for the purpose of improving film properties and developability. The alkali-soluble resin that can be used in the present invention is a linear organic polymer, and at least 1 in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having two groups that promote alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).
More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in Japanese Unexamined Patent Publication Nos. 59-53836 and 59-71048. Acrylic copolymers such as acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having carboxylic acids in the side chains, and polymers having hydroxyl groups with acid anhydrides added. Can be mentioned.
The acid value is preferably in the range of 20 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g, more preferably 35 to 120 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
As the alkyl (meth) acrylate and aryl (meth) acrylate, CH ₂ ═C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, 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 (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferred. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains are, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Poly (ethylene glycol-propylene glycol) mono (meth) acrylate and the like, and compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol) -An acrylic copolymer having propylene glycol) mono (meth) acrylate or the like as a copolymerization component.

In addition, as the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. Represents. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
These other copolymerizable monomers can be used singly or in combination of two or more. Other preferable copolymerizable monomers are alkyl (meth) acrylate (alkyl is an alkyl group having 2 to 4 carbon atoms), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.

As already described, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is so small that it takes too much time for development, which is not preferable.
In addition, the weight average molecular weight Mw of the acrylic resin (polystyrene conversion value measured by the GPC method) is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. It is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000.
In order to make the acid value of acrylic resin into the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer. Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized.
The acrylic resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic resin by radical polymerization can be easily set by those skilled in the art. Is possible.

  The addition amount when the alkali-soluble resin is added to the curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. When the amount of the alkali-soluble resin is less than 5% by mass, the film strength is lowered. When the amount is more than 90% by mass, the acid content increases, so that it becomes difficult to control the solubility and the pigment is relatively reduced. Therefore, sufficient image density cannot be obtained. It is preferable at the point which becomes easy to obtain the coating film of thickness. In particular, a good coating can be obtained with a high yield for slit coating suitable for coating on a wide substrate having a large area.

Further, in order to improve the crosslinking efficiency of the photocurable coloring composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group, Polymers containing an aryl group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain are useful.
The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting.
Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as alkali-soluble groups such as COOH groups and OH groups and carbon-carbon unsaturated bonds are included.
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

The acid value of the alkali-soluble resin having a polymerizable double bond in the present invention is preferably 30 to 150 mgKOH / g, more preferably 35 to 120 mgKOH / g, and the mass average molecular weight Mw is preferably 2,000 to 50,000, more preferably 3,000 to 30,000.
As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used. Examples of compounds having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

The curable composition of this invention may further contain the component explained in full detail as needed.
<Dispersant>
In the curable composition of the present invention, when (E) a pigment is contained, from the viewpoint of improving the dispersibility of the pigment, (A) a main chain part having a nitrogen atom and a graft chain part having an oxyalkylene part A dispersant other than the resin may be further added. Addition of a dispersant improves the dispersion performance.
Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) Derivatives) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, Enomoto Kasei “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, manufactured by Kao Corporation DEMAL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920 , 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (Stearylamine Acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000 , 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemical Co., Ltd., and the like.

These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. As content of the dispersing agent in this invention, it is preferable that it is 1 mass%-100 mass% with respect to a pigment, 3 mass%-100 mass% are more preferable, 5 mass%-80 mass% are still more preferable. .
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5% by mass to 100% by mass and more preferably in the range of 10% by mass to 80% by mass with respect to the pigment. preferable. In the case of using a pigment derivative, the amount used is preferably in the range of 1% by mass to 30% by mass with respect to the pigment, and more preferably in the range of 3% by mass to 20% by mass. It is preferably in the range of 5% by mass to 15% by mass.

  In the present invention, when a pigment and a dispersant are used, the total content of the pigment and the dispersant is 35% by mass or more based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.

<Sensitizer>
The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable. Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
In addition, European Patent No. 568,993, U.S. Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And compounds described in Japanese Patent No. 271969.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in the present invention, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and sensitizers that can improve the ink inking property on the surface of the photosensitive layer, substrate adhesion You may add the board | substrate adhesion agent which can improve this.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

When the curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”) is added. May be.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesion agent is 0.1% by mass or more and 30% by mass with respect to the total solid content of the curable composition of the present invention from the viewpoint of leaving no residue in the unexposed part of the curable composition. % Or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.
Further, the curable composition of the present invention can form a colored region having excellent pigment dispersion stability and developability, high definition and good color characteristics even when containing a fine pigment at a high concentration. The production of a color filter for a solid-state imaging device, particularly when forming a pixel having a film thickness of 0.8 μm or less, preferably a film thickness of 0.1 μm or more and 0.6 μm or less, particularly the pigment of the present invention. It can be said that the effect is remarkable by using the contained colored curable composition.

(Preparation of colored curable composition)
Hereinafter, the preferable manufacturing method in the case of adding the (E) pigment to the curable composition of the present invention to obtain a colored curable composition will be described.
(E) In the curable composition of the present invention including a pigment, first, (A) a resin having a main chain portion including a nitrogen atom and a side chain portion including an oxyalkylene group; (E) After performing the first step of preparing a pigment dispersion containing a pigment, other components, specifically, (B), a photopolymerization initiator, (C) an ethylenically unsaturated double bond It is preferable to prepare by performing the 2nd process of mixing the compound containing this, (D) solvent, and other additives used together together as desired, such as surfactant.

In the first step, when preparing a pigment dispersion liquid composition, the pigment content in the pigment dispersion is preferably 35% by weight or more and 95% by weight or less, and 40% by weight or more and 80% by weight or less based on the total solid content. Most preferably: (A) The specific resin is preferably 5% by weight or more and 50% by weight or less, and preferably 10% by weight or more and 30% by weight or less, based on the total solid content in the pigment dispersion.
Next, in the second step of preparing a colored curable composition using this pigment dispersion, the content of the pigment dispersion contained in the colored curable composition is appropriately adjusted according to the amount of pigment required. However, generally, it is preferably 5 to 50% by weight, and most preferably 10 to 40% by weight, based on the curable composition. In this 2nd process, components other than (A) component and (E) component are mixed, and the curable composition of this invention can be obtained by stirring. By preparing by including such first and second steps, the resulting curable composition has a dispersibility and dispersion stability of the pigment as compared with the case of directly adding and mixing the (E) pigment. Is further improved.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed using the curable composition of the present invention on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on the support, and exposure for exposing the colored layer through a mask And a developing step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored layer forming step>
In the colored layer forming step, a colored layer made of the curable composition is formed on the support by applying the curable composition of the present invention and containing the (E) pigment.

Examples of the support that can be used in this step include a photoelectric conversion element substrate used for an imaging element or the like, such as a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like. In some cases, a black matrix for isolating each pixel is formed on these substrates.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

Examples of the coating method of the curable composition of the present invention on the support include slit coating, ink jet method, spin coating, cast coating, roll coating, coil bar coating, screen printing method, gravure printing method, and reverse printing method. Various coating methods can be applied.
The film thickness immediately after application of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2-3 micrometers is more preferable.

  The colored layer (curable composition layer) applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like.

As a coating film thickness after drying of the curable composition (hereinafter referred to as “dry film thickness” as appropriate), in order to use it as a color filter for a solid-state image sensor, light in an oblique direction is used from the viewpoint of securing color density. From the viewpoint of reducing problems such as not reaching the light receiving portion and a significant difference in the light collection rate between the edge and the center of the device, it is preferably 0.05 μm or more and less than 1.0 μm, preferably 0.1 μm or more and 0 0.8 μm or less is more preferable, and 0.2 μm or more and 0.7 μm or less is particularly preferable.
In order to use as a color filter for a display element, from the viewpoint of light transmittance and contrast, it is preferably 0.5 μm or more and 3.0 μm or less, and is preferably in a range of 1.0 μm or more and 2.5 μm or less. Most preferred.

<Exposure process>
In the exposure step, the colored layer (curable composition layer) formed in the colored layer forming step is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, and developed with a developer. And it can carry out by forming the pattern-form film | membrane which consists of a pixel of each color (3 colors or 4 colors). As the radiation that can be used for exposure, ultraviolet rays such as i-line (365 nm) are preferably used, and as the exposure machine, a stepper exposure machine in which the exposure light becomes parallel rays is preferable.
Proximity exposure machines with broad exposure light are not preferable because it is difficult to obtain the expected effect. Irradiation dose is more preferably preferably ^{50~1000mJ / cm 2 30~1500mJ / cm 2} , and most preferably 80~500mJ / cm ^2.

<Development process>
Subsequently, by performing an alkali development process (development process), the light non-irradiated part is eluted in the alkaline aqueous solution by the exposure, and only the photocured part remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, 0] -7-undecene and the like, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. The concentration of these alkali agents is 0.001% by mass to 10%. An alkaline aqueous solution diluted with pure water so as to have a mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried.

  In the production method of the present invention, after the colored layer forming step, the exposure step, and the development step described above are performed, the formed colored pattern is cured by heating (post-baking) and / or exposure as necessary. A curing step may be included.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the colored layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as in the above pixel production method except that a black pigment such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

  Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition has excellent development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a high-resolution CCD device or CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

(Synthesis Example 1)
[Specific resin: Synthesis of resin (A)]
50 g of polyethyleneimine (number average molecular weight 600) and 1.0 g of powdered sodium hydroxide were added to a 1.0 L autoclave and heated to 80 ° C. Then, nitrogen substitution was performed 3 times and it heated at 170 degreeC.
Next, a total of 500 g of ethylene oxide was added over 5 hours so as not to exceed 0.5 MPa, and then heated for 2 hours. After cooling to 80 ° C., the mixture was stirred for 1 hour under a nitrogen stream, unreacted ethylene oxide was removed from the reaction system, and then cooled to room temperature to obtain 540 g of resin (A) having the following structure. In the following, the numerical values written in the respective structural units in the resin structure indicate the degree of polymerization.
As a result of measuring the average molecular weight of the obtained polymer compound by a gel permeation chromatography (GPC) method using polystyrene as a standard substance, the mass average molecular weight (Mw) was 13,100.

(Synthesis Example 2)
[Specific Resin: Synthesis of Resin (B)]
50 g of polyallylamine (number average molecular weight 3,000) and 1.0 g of powdered sodium hydroxide were added to a 1.0 L autoclave and heated to 80 ° C. Then, nitrogen substitution was performed 3 times and it heated at 170 degreeC.
Next, a total of 500 g of propylene oxide was added over 5 hours so as not to exceed 0.5 MPa, and then heated for 2 hours. After cooling to 80 ° C., the mixture was stirred for 1 hour under a nitrogen stream, unreacted ethylene oxide was removed from the reaction system, and then cooled to room temperature to obtain 540 g of resin (B) having the following structure.
As a result of measuring the molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, the mass average molecular weight was 11,500.

(Synthesis Example 3)
[Specific resin: Synthesis of resin (C)]
50 g of polyethyleneimine (number average molecular weight 1800) and 1.0 g of powdered sodium hydroxide were added to a 1.0 L autoclave and heated to 80 ° C. Then, nitrogen substitution was performed 3 times and it heated at 170 degreeC.
Next, a total of 250 g is added over 2.5 hours so that ethylene oxide does not exceed 0.5 MPa, and then a total of 250 g is added over 2.5 hours so that propylene oxide does not exceed 0.5 MPa, Then, it heated for 2 hours. Next, after cooling to 80 ° C., the mixture was stirred for 1 hour under a nitrogen stream, unreacted ethylene oxide was removed from the reaction system, and then cooled to room temperature to obtain 540 g of resin (C) having the following structure.
As a result of measuring the molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, the mass average molecular weight was 12,500.

(Synthesis Example 4)
[Specific Resin: Synthesis of Resin (D)]
Tetrahydrofuran solution containing 20 g of the resin (A) obtained in Synthesis Example 1 and 7.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene and 50 g of N-methylpyrrolidinone and 12.5 g of palmitic acid chloride. 50 mL was slowly added dropwise and stirred at room temperature for 5 hours. Thereafter, the reaction solution was added to 1.0 L of water, and the precipitated powder was collected by filtration and dried to obtain 24 g of resin (D) having the following structure.
As a result of measuring the molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, the mass average molecular weight was 8,500.

(Synthesis Example 5)
[Specific Resin: Synthesis of Resin (E)]
45 g of palmitic acid, 200 g of 6-hexanolactone and 0.1 g of tetrabutyl orthotitanate were heated at 170 ° C. for 15 hours and allowed to cool to obtain 240 g of polyester (A). Next, 50 g of polyethyleneimine (number average molecular weight 1,800) and 100 g of polyester (α) were heated at 170 ° C. for 5 hours and allowed to cool to obtain 145 g of polyimine (β) having polyester as a graft chain. 50 g of this polyimine (β) and 1.0 g of powdered sodium hydroxide were added to a 1.0 L autoclave and heated to 80 ° C. Then, nitrogen substitution was performed 3 times and it heated at 170 degreeC.
Next, a total of 500 g of propylene oxide was added over 5 hours so as not to exceed 0.5 MPa, and then heated for 2 hours. After cooling to 80 ° C., the mixture was stirred for 1 hour under a nitrogen stream, unreacted ethylene oxide was removed from the reaction system, and then cooled to room temperature to obtain 540 g of resin (E) having the following structure.
As a result of measuring the molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, the mass average molecular weight was 16,500.

(Synthesis Example 6)
[Synthesis of Comparative Resin (F)]
100 g of the polyester (α) obtained in Synthesis Example 5 and 10 g of polyethyleneimine (number average molecular weight 1,800) were heated at 170 ° C. for 5 hours and allowed to cool, and then 105 g of a comparative resin (F) having the following structure was obtained. .

  The obtained resins (A) to (F) were prepared as propylene glycol monomethyl ether acetate solutions having a solid content of 20% by weight.

[Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-3]
<Example used for forming color filter for liquid crystal display>
[1. Preparation of curable composition]
Here, an example in which a curable composition containing a pigment is prepared for forming a color filter for use in a liquid crystal display element will be described.

1-1. Preparation of pigment dispersion (pigment dispersion composition)
(E) Pigment (Amount listed in Table 1)
(C.I. Pigment Green 36 and C.I. Pigment Yellow 219
30/70 (mass ratio) mixture with (average particle diameter 61 nm)),
・ (A) Specific resin (Amounts listed in Table 1)
(Resins (A) to (E): Resins listed in Table 1 (solid content concentration 20% by weight)
・ Alkali-soluble resin (Amount listed in Table 1)
(Benzyl methacrylate / methacrylic acid copolymer (mol ratio 70/30,
30% by weight solution of propylene glycol monomethyl ether acetate having a weight average molecular weight of 7,000)
-(D) Solvent [Propylene glycol monomethyl ether acetate] 110 parts by mass The above composition was mixed and mixed and dispersed for 5 hours by a bead mill to prepare a pigment dispersion. Here, (A) specific resin which concerns on this invention functions as a pigment dispersant.
The average particle diameter of the pigment in the obtained dispersion was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and the results are shown in Table 1.

1-2. Preparation of curable composition (coating liquid) A curable composition solution was prepared by stirring and mixing the pigment dispersion liquids 1 to 8 having been subjected to the dispersion treatment so as to have the following composition ratio.
Colorant (Pigment dispersions 1 to 8: dispersions listed in Table 1) 600 parts by mass Photopolymerization initiator [component (B)] 30 parts by mass (2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole)
Pentaerythritol tetraacrylate [component (C)] 50 parts by weight Alkali-soluble resin 20 parts by weight (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000)
・ Solvent [component (D)] 900 parts by mass (propylene glycol monomethyl ether acetate)
-Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass-Sensitizer (the following compound α) 15 parts by mass-Co-sensitizer (2-mercaptobenzimidazole) 15 parts by mass

[Production of color filters]
1-3. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).

(Slit application conditions)
・ Gap of the opening at the tip of the coating head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
-Dry film thickness: 1.75 μm
・ Application temperature: 23 ℃

1-4. Exposure and development Thereafter, the curable composition film is exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is organically developed. The sample was covered with a 10% aqueous solution (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and left still for 60 seconds.

1-5. Heat treatment After standing still, pure water was sprayed in the form of a shower to wash away the developer, and the coating film subjected to such exposure (photocuring) treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the color filter formed by forming a curable composition coating film (colored layer) on the glass substrate was obtained.

1-6. Performance Evaluation The dispersibility, dispersion stability and developability of the curable composition coating film (colored layer) formed on the glass substrate using the curable composition prepared above were evaluated as follows. The results are shown in Table 2.

<Dispersibility>
After preparing the pigment dispersion, the viscosity was measured and the dispersibility was evaluated. The lower the viscosity, the better the dispersibility of the pigment.
-Evaluation criteria-
○: Viscosity of less than 10 mPa · s Δ: Viscosity of 10 mPa · s or more and less than 15 mPa · s ×: Viscosity of 15 mPa · s or more <Dispersion stability>
The viscosity was measured 7 days after the preparation of the pigment dispersion, and the dispersion stability was evaluated. The lower the viscosity increase rate, the better the dispersion stability of the pigment over time.
-Evaluation criteria-
○: Increase in viscosity is less than 10% Δ: Increase in viscosity is 10% or more and less than 30% ×: Increase in viscosity is 30% or more

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability. The smaller the residue, the better the developability.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Evaluation of contrast of liquid crystal display element>
A colored curable composition containing the pigment dispersion composition was applied on a glass substrate to a thickness of 2 μm to prepare a sample. When a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is used as a backlight unit and two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) are parallel The transmitted light amount with respect to the vertical direction was measured, and the ratio of the transmitted light amount when the polarization axis was parallel to the transmitted light amount when the polarization axis of the polarizing plate was vertical was defined as contrast. The evaluation criteria are as follows.
○: Contrast 6000 or more ×: Contrast 6000 or less

From the results of Table 2, the curable compositions of Examples 1-1 to 1-5 containing the specific resin (A) in the present invention have good dispersibility, dispersion stability, and developability, and are cured. It can be seen that the composition is excellent as an adhesive composition. Moreover, it turns out that the coloring area | region by this curable composition has a favorable contrast, and is useful for preparation of the color filter for liquid crystal display elements excellent in contrast.
On the other hand, the curable compositions of Comparative Examples 1-1 to 1-3 using a known dispersant [Comparative Resin (F)] are dispersed even if the ratio of the alkali-soluble resin and the known dispersant is variously changed. Those with good dispersibility and dispersion stability are inferior in developability, those with good developability have low dispersibility and dispersion stability, and it is difficult to make all of these properties good, and high-definition color filters It turned out that it is unsuitable for producing.

[Examples 2-1 to 2-5, Comparative examples 2-1 to 2-3]
<Examples used for forming color filters for solid-state imaging devices>
Hereinafter, an example of preparing a curable composition containing a colorant (pigment) for forming a color filter for use in a solid-state imaging device will be described.

2-1. Preparation of pigment dispersion (pigment dispersion composition)
(E) Pigment (Amount described in Table 3)
(C.I. Pigment Green 36 and C.I. Pigment Yellow 219
30/70 (mass ratio) mixture with (average particle diameter 61 nm)),
・ (A) Specific resin (Amounts listed in Table 3)
[Resin (A) to (E): Resins listed in Table 3 (solid content concentration: 20% by weight)]
・ Alkali-soluble resin (Amounts listed in Table 3)
(Benzyl methacrylate / methacrylic acid copolymer (mol ratio 70/30,
30% by weight solution of propylene glycol monomethyl ether acetate having a weight average molecular weight of 7,000)
-(D) Solvent [Propylene glycol monomethyl ether acetate] 110 parts by mass The above composition was mixed and mixed and dispersed for 5 hours by a bead mill to prepare a pigment dispersion. Here, (A) specific resin which concerns on this invention functions as a pigment dispersant.
The average particle diameter of the pigment in the obtained dispersion was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and the results are shown in Table 3.

2-2. Preparation of curable composition (coating liquid) A curable composition solution was prepared by stirring and mixing the pigment dispersion liquids 9 to 16 subjected to the dispersion treatment so that the following composition ratio was obtained.
Colorant (pigment dispersions 9 to 16: listed in Table 3) 600 parts by mass Photopolymerization initiator [(B): Oxime-based photopolymerization initiator] 30 parts by mass (CGI-124, Ciba Specialty Chemicals) Made)
Dipentaerythritol hexaacrylate [component (C)] 30 parts by mass Component C (TO-1382 (manufactured by Toagosei Co., Ltd.)) 25 parts by mass (D) 900 parts by mass of solvent (PGMEA) Agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass

2-3. Preparation of color filter with curable composition <Preparation of silicon substrate with undercoat layer>
A resist solution for preparing a silicon substrate with an undercoat layer was prepared according to the following composition.
-Propylene glycol monomethyl ether acetate 19.20 parts by mass-Ethyl lactate 36.67 parts by mass-Resin (benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 40% PGMEA solution) 30.51 parts by mass-ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate)
12.20 parts by mass-polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass-fluorine-based surfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts by mass (B) Photopolymerization initiator (trihalomethyltriazine photopolymerization initiator) 0.586 parts by mass (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

  A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Got.

The coloring agent containing curable composition prepared according to Table 3 was apply | coated on the undercoat layer of the silicon wafer with undercoat layer, and the colored layer (coating film) was formed. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, exposure was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) at a wavelength of 365 nm and through an Island pattern mask having a pattern of 2 μm square at various exposure amounts of 50 to 1200 mJ / cm ² .
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.

2-4. Performance Evaluation The dispersibility, dispersion stability and developability of the curable composition coating film (colored layer) formed on the silicon wafer substrate using the curable composition prepared above are the same as in Example 1-1. And evaluated. Moreover, the color unevenness of the formed coloring pattern was evaluated as follows.

<Color unevenness of solid-state image sensor>
The color unevenness was evaluated by analyzing the luminance distribution by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.
A method for measuring the luminance distribution will be described.
First, the curable composition was applied onto the undercoat layer of the glass plate with the undercoat layer to form a colored layer (coating film). Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
The brightness | luminance distribution of the glass plate which apply | coated this curable composition and formed the colored layer analyzed the image | photographed with microscope MX-50 (made by Olympus).
-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels × : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels.

From the results of Table 4, the curable compositions of Examples 2-1 to 2-5 containing the specific resin (A) in the present invention are the same as the colored curable composition for forming a color filter for liquid crystal display. It can be seen that the dispersibility, dispersion stability and developability are all good, and the composition is excellent as a curable composition. In addition, it can be seen that the colored layer made of this curable composition has no deviation in luminance distribution and is useful for forming uniform colored pixels, and thus for producing a high-contrast and high-definition color filter for a solid-state imaging device.
On the other hand, the curable compositions of Comparative Examples 2-1 to 2-3 using the known dispersant [Comparative Resin (F)] are dispersed even if the ratio of the alkali-soluble resin and the known dispersant is variously changed. Those with good dispersibility and dispersion stability are inferior in developability, those with good developability have low dispersibility and dispersion stability, and it is difficult to make all of these properties good, and high-definition color filters Turned out to be unsuitable to create.

  As described above, it is apparent that the curable composition of the present invention is excellent in all of the dispersibility, dispersion stability, and developability necessary for producing color filters for liquid crystal displays and solid-state imaging devices.

Claims (8)

  (A) a resin having a main chain part containing a nitrogen atom and a side chain part containing an oxyalkylene group, (B) a photopolymerization initiator, (C) a compound containing an ethylenically unsaturated double bond And (D) a curable composition containing a solvent.   Furthermore, (E) A pigment is contained, The curable composition of Claim 1 characterized by the above-mentioned.   (A) a pigment dispersion prepared by including a resin having a main chain part containing a nitrogen atom and a side chain part having an oxyalkylene group, and (E) a pigment, and (B) initiation of photopolymerization. The curable composition according to claim 2, obtained by mixing an agent, a compound containing (C) an ethylenically unsaturated double bond, and (D) a solvent.   Furthermore, (F) alkali-soluble resin is contained, The curable composition of any one of Claim 1 to 3 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 4, wherein the main chain portion including the nitrogen atom includes a polyamine structure.   A color filter comprising a colored region formed of the curable composition according to any one of claims 2 to 5 on a support.   A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition according to any one of claims 2 to 5 on a support, and the colored layer A color filter manufacturing method comprising: an exposure step of pattern exposure through a mask; and a development step of developing a colored layer after exposure to form a colored pattern.   A solid-state image sensor provided with the color filter obtained by the manufacturing method of the color filter of Claim 7.