JP5317809B2 - Colored curable composition, colored pattern forming method, color filter, and liquid crystal display device - Google Patents

Abstract

The present invention provides a colored curable composition, a method of forming a colored pattern, a color filter with a high image analysis degree and without pixel of non-even color, and a liquid crystal display device, wherein the colored curable composition is capable of forming the colored pattern with good linearity and without gaps, developing latitude of forming the pattern is great, and non-even color of the colored pattern caused by the following baking process may be avoided. The colored curable composition contains a compound (A1) represented by formula (I), an united imidazole compound (A2), a polymerized compound (B), a colorant (C) and an alkali-soluble bond resin (D) with double keys in a side chain. In the formula (I), R, B0 and Q represent univalence organic groups respectively, Z represents a hydrogen atom or a univalence substituent, and n2 is an integer from 0 to 5.

Description

  The present invention relates to a colored curable composition, a colored pattern forming method, a color filter, and a liquid crystal display device.

Examples of the colored curable composition include those obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since such a colored curable composition is polymerized and cured by irradiation with light, it is used in photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.
Moreover, as a colored curable composition, the other aspect which generate | occur | produces an acid by irradiation of light and uses the generated acid as a catalyst is also known, for example. Specifically, using a coloring reaction of a dye precursor catalyzed by the generated acid, a material for image formation, anti-counterfeiting, energy dose detection, a semiconductor utilizing a decomposition reaction catalyzed by the generated acid It is used for positive type resists for manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing and the like.

  In recent years, colored curable compositions that are particularly sensitive to light sources of short wavelengths (365 nm and 405 nm) have been desired for various applications, and compounds exhibiting excellent sensitivity to such short wavelength light sources, for example, There is an increasing demand for photopolymerization initiators. However, since a photopolymerization initiator having excellent sensitivity generally lacks stability, a photopolymerization initiator that satisfies the improvement in sensitivity and the stability over time is desired.

Therefore, oxime ester derivatives are proposed in the following Patent Documents 1 to 4 as photopolymerization initiators used in the colored curable composition. However, since these known oxime ester derivatives have low absorbance at a wavelength of 365 nm and a wavelength of 405 nm, they are still not satisfactory in terms of sensitivity.
In addition, as a colored curable composition, there is a demand for a colored curable composition that is excellent in stability with time and has excellent sensitivity to light having a short wavelength such as 365 nm and 405 nm.
Furthermore, although a colored radiation-sensitive composition for a color filter containing an oxime compound having a specific structure is disclosed (see, for example, Patent Document 5), with respect to stability over time and sensitivity to light of a short wavelength. It was still inadequate. Moreover, in the colored curable composition for color filters, the reproducibility of the hue after pattern formation is a new problem, and improvement of the problem that the colorability changes with time has been strongly desired.

On the other hand, a color filter for a liquid crystal display device has a strong demand for a high color density of the color filter in order to expand a color reproduction region. When a large amount of a colorant is added to obtain a high coloring density, the sensitivity is insufficient, and there is a tendency for pattern loss to occur frequently as a whole. In order to eliminate this loss, it is necessary to irradiate light with higher energy, so that the exposure time becomes longer and the manufacturing yield is significantly reduced. From the above, regarding a colored curable composition for a color filter, a good pattern forming property is desired while containing a colorant at a high concentration.
Furthermore, when forming a colored pattern in the color filter manufacturing process, a post-heat treatment, so-called post-bake process, is generally performed to improve the effectiveness, but color unevenness occurs at the pattern edge after the heat treatment. It turns out that there is a problem to do.
US Pat. No. 4,255,513 US Pat. No. 4,590,145 JP 2000-80068 A JP 2001-233842 A JP 2006-195425 A

The first object of the present invention is a color polymerization in which a linear pattern having good linearity is formed, a chipped colored pattern is formed, the development latitude at the time of pattern formation is wide, and color unevenness of the colored pattern in the post-baking process is suppressed. It is to provide a sex composition.
A second object of the present invention is to provide a method for forming a colored pattern having good pattern forming properties, a wide development latitude, and excellent productivity.
Furthermore, a third object of the present invention is to provide a color filter having a colored pattern with no color unevenness, high resolution and good pattern shape, and a liquid crystal display device provided with the color filter.

As a result of intensive studies, the present inventors have solved the above problems by using an oxime compound and a biimidazole compound having a specific structure and a binder resin having a specific structure. Specific means for solving the problem will be described below.
<1> (A1) A compound represented by the following general formula (1), (A2) a biimidazole compound, (B) a polymerizable compound, (C) a colorant, and (D) having a double bond in a side chain. A colored curable composition containing an alkali-soluble binder resin.

In the general formula (I), R, B ⁰ and Q each independently represent a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 0 to 5. .
<2> The colored curable composition according to <1>, wherein the (C) colorant is a pigment and further contains (E) a pigment dispersant.
<3> A step of forming a colored curable composition layer using the colored curable composition according to <1> or <2>, and a step of exposing and curing the colored curable composition layer in a pattern. And a step of developing the colored curable composition layer after the exposure to remove an uncured colored curable composition portion to form a colored pattern.
<4> A color filter having a colored pattern formed on the support using the method according to <3>.
<5> A liquid crystal display device comprising the color filter according to <4>.

According to the present invention, a colored polymerizable composition having good linearity, forming a colored pattern having no chip, having a wide development latitude during pattern formation, and suppressing color unevenness of the colored pattern due to the post-baking process. Is provided.
In addition, according to the present invention, there is provided a method for forming a colored pattern having good pattern forming properties, wide development latitude, and excellent productivity.
Furthermore, according to the present invention, it is possible to provide a color filter having a color pattern with no color unevenness and a high resolution and good pattern shape, and a liquid crystal display device including the color filter.

The photomicrograph used as the standard of color unevenness judgment of the coloring pattern produced using the colored polymerizable composition of the present invention is shown, and (A) is a judgment example that there is no shading in the pattern and “no color unevenness”. , (B) is an example of determination that color shading is confirmed in the pattern and “there is uneven color”.

Hereinafter, a colored curable composition of the present invention, a colored pattern forming method using the colored curable composition, a color filter having the colored pattern, a liquid crystal display device using the color filter, and a solid-state imaging device This will be described in detail.
<< Colored curable composition >>
The colored curable composition of the present invention comprises (A1) a compound represented by the general formula (1) (hereinafter sometimes referred to as a specific oxime compound), (A2) a biimidazole compound (B) a polymerizable compound, And (C) a colorant and (D) an alkali-soluble binder resin having a double bond in the side chain.
First, the colored curable composition of the present invention will be described.

<(A1) Compound Represented by General Formula (1)>

In general formula (I), R, ^B0 , and Q each independently represent a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 0-5.

  In the present invention, (A1) the compound represented by the general formula (I) (hereinafter appropriately referred to as a specific oxime compound) is decomposed by light, and initiates and accelerates polymerization of the polymerizable compound (B) described later. It has a function as a photopolymerization initiator. In particular, since the specific oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm, it exhibits excellent effects when used as a photopolymerization initiator in combination with a polymerizable compound in a colored curable composition.

  The colored curable composition of the present invention has high sensitivity to light having a wavelength of 365 nm or 405 nm, is excellent in stability over time, and can form a cured film that can suppress coloring over time. Although the detailed mechanism is unknown, the specific oxime compound has a structure that absorbs light and suppresses radical recombination when cleaved, so that the amount of generated radicals is large and high sensitivity can be achieved. . Moreover, from the point that radical recombination is suppressed, it is considered that the reaction between the decomposition products of the specific oxime compound is suppressed during heating and coloration derived from the reaction is suppressed.

In the present invention, the color difference ΔE ^* ab may be used to evaluate the coloration of the cured film over time. Here, the color difference ΔE ^* ab can be measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
As conditions for the evaluation, firstly, a range of colored curable composition ultra-high pressure mercury lamp proximity-type exposure apparatus, or i-line stepper exposure device (365 nm) of 10mJ ^/ cm ² ~2500mJ ^/ cm 2 of the present invention A cured film is formed by exposure with various exposure amounts. Then, after developing as desired, the cured film is heated at 200 ° C. for 1 hour.
By measuring the color difference ΔE ^* ab before and after heating the cured film, the colored state of the cured film due to heating can be evaluated.
When the colored curable composition of the present invention is used, the color difference ΔE ^* ab before and after heating can be 3 or less, the color change due to heating can be greatly reduced, and a color filter with high color purity can be obtained.

  The specific oxime compound of the present invention can be synthesized, for example, by the method described in JP-A-2007-269778 [0067] to [0069], but is not limited thereto.

In the general formula (I), R represents a monovalent organic group.
Examples of the monovalent organic group represented by R in the general formula (I) include an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkenyl which may have a substituent. Group, optionally substituted alkynyl group, optionally substituted alkylsulfinyl group, optionally substituted arylsulfinyl group, optionally substituted alkylsulfonyl group, substituted An arylsulfonyl group which may have a group, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a substituent Phosphinoyl group which may have, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, having a substituent Dial Le aminocarbonyl group, a substituent include good dialkylaminothiocarbonyl group. Among these, acyl groups are preferred which may have a substituent.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, etc. are mentioned.
The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. .
As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a propylsulfinyl group.
The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, and a 2-naphthylsulfinyl group.
The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group.
The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, and a 2-naphthylsulfonyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.
Examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic group containing a hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Examples of the heterocyclic group include thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, and xanthenyl group. And phenoxathiinyl group.

Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.
Examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, and a 4-methylsulfanylphenylthiocarbonyl group.

Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.
Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, a dibutylaminothiocarbonyl group, and the like.

  Among these, the monovalent organic group represented by R is more preferably an acyl group from the viewpoint of high sensitivity, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, a toluyl group. Is preferred.

  As specific examples of the monovalent organic group represented by R in the general formula (I), those shown below are preferable from the viewpoint of increasing sensitivity.

In the general formula (I), examples of the monovalent organic group represented by B ⁰ include a phenyl group which may have a substituent and an alkyl group having 1 to 20 carbon atoms which may have a substituent. , An alkenyl group having 1 to 20 carbon atoms which may have a substituent, an alkynyl group having 1 to 20 carbon atoms which may have a substituent, and 5 carbon atoms which may have a substituent. 8 cycloalkyl group, an optionally substituted alkanoyl group having 2 to 20 carbon atoms, an optionally substituted benzoyl group, and optionally having 2 to 12 carbon atoms An alkoxycarbonyl group, an optionally substituted phenoxycarbonyl group, —S (O) m—R ¹² (wherein R ¹² represents an alkyl group having 1 to 6 carbon atoms, and m represents 0 to 2). is an integer), -. S (O) m-R 13 ( ^{wherein, R 13} is a carbon number 6-1 2 represents an aryl group, may be substituted with an alkyl group having 1 to 12 carbon atoms, and m is an integer of 0 to 2.), an alkoxy having 1 to 6 carbon atoms which may have a substituent. Examples thereof include a sulfonyl group, an aryloxysulfonyl group having 6 to 10 carbon atoms and a diphenylphosphinoyl group which may have a substituent.

In the general formula (I), when B ⁰ represents a phenyl group, the substituent that can be introduced is an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR ⁸ , —SR ⁹ or —N ( R ¹⁰ ) (R ¹¹ ) may be mentioned, and a plurality of these substituents may be included.
In the case where B ⁰ represents an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 11 carbon atoms, It may have one or more oxygen atoms or S atoms between the constituent carbon atoms, or may be substituted with one or more hydroxy groups.
When B ⁰ represents a benzoyl group or a phenoxycarbonyl group, examples of the substituent that can be introduced include an alkyl group having 1 to 6 carbon atoms, a phenyl group, —OR ⁸ , —SR ⁹ or —N (R ¹⁰ ) ( R ¹¹ ), and two or more of these may be included.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted alkyl group having 2 to 6 carbon atoms [provided that the substituent is a hydroxy group, a mercapto group, a cyano group, or an alkyl group having 1 to 4 carbon atoms. An alkoxyl group, an alkenyloxy group having 3 to 6 carbon atoms, a 2-cyanoethoxy group, a 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, a phenylcarbonyloxy group, It consists of one or more of a carboxyl group or a C2-C5 alkoxycarbonyl group. ], The alkyl group having 2 to 6 carbon atoms having one or more oxygen atoms between carbon atoms constituting the main chain, alkanoyl group having 2 to 8 carbon _{atoms, - (CH 2 CH 2 O} ) nH ( where, n Is an integer of 1 to 20), an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom) Or a phenylalkyl group having 7 to 9 carbon atoms, —Si (R ¹⁴ ) r (R ¹⁵ ) ₃ —r (wherein R ¹⁴ has 1 to 1 carbon atoms) 8 represents an alkyl group, R ¹⁵ represents a phenyl group, and r represents an integer of 1 to 3.

R ^{9 to} R ¹¹ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, a substituted alkyl group having 2 to 6 carbon atoms {provided that the substituent is Hydroxy group, mercapto group, cyano group, alkoxy group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, carbon It consists of one or more of a 2-5 alkylcarbonyloxy group, a phenylcarbonyloxy group, a carboxyl group, or a C2-C5 alkoxycarbonyl group. }, An alkyl group having 2 to 12 carbon atoms having at least one oxygen atom or sulfur atom between carbon atoms constituting the main chain, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms or a carbon number) 1 to 4 alkoxyl groups may be substituted.), A phenylalkyl group having 7 to 9 carbon atoms.

  In general formula (I), Z represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent represented by Z include a halogen group such as a fluorine atom; a methoxy group, an ethoxy group, alkoxy groups such as tert-butoxy group; aryloxy groups such as phenoxy group; alkoxycarbonyl groups such as methoxycarbonyl group; acyloxy groups such as acetoxy group; acyl groups such as acetyl group and benzoyl group; alkylsulfanyl groups such as methylsulfanyl group An arylsulfanyl group such as a phenylsulfanyl group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dialkylamino group such as a dimethylamino group; an arylamino group such as a phenylamino group or a p-tolylamino group; Alkyl groups such as ethyl group, tert-butyl group, dodecyl group In addition to aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p- Toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumumyl group, dimethylsulfoniumumyl group, triphenylphenacylphosphoniumyl group And a cyano group.

As the monovalent substituent represented by Z in the general formula (I), an alkoxy group, an alkylamino group, an arylamino group, an alkyl group, and an aryl group are preferable.
Z in formula (I) is preferably a hydrogen atom or the monovalent substituent described above.

n2 represents the integer of 0-5, 0-3 are preferable and 0 or 1 is more preferable.
When n2 represents an integer of 2 to 5, Z may be the same substituent or different substituents.
Examples of the structure represented by the following general formula (I-1) excluding the oxime ester structure in the compound represented by the general formula (I) are shown below.

Although the specific example of a compound represented by general formula (I) below is shown, it is not limited to these.
The compound represented by the general formula (I) has a molar extinction coefficient at 365 nm of 12,000 to 500,000. All of the specific examples shown below have a molar extinction coefficient in the range of 12,000 to 500,000.

The oxime polymerization initiator represented by the general formula (I) has a maximum absorption wavelength in a region near 365 nm and is a compound having high absorption efficiency with respect to light having a wavelength of 365 nm.
The specific oxime compound represented by general formula (I) may be used individually by 1 type in a colored curable composition, and may use 2 or more types together.
(A1) As content in the colored curable composition of a specific oxime compound, it is 0.1 with respect to 100 parts of total solid content of this colored curable composition in terms of mass from a viewpoint of sclerosis | hardenability and colorability. Parts to 8.0 parts are preferred, and more preferably 0.5 parts to 6.0 parts.

<(A2) Biimidazole Compound>
The colored curable composition of the present invention further needs to contain (A2) a biimidazole compound. (A2) The biimidazole compound is a compound having the function of decomposing by exposure in the wavelength region of 300 nm to 500 nm to cause and advance polymerization of the polymerizable compound described later, as in the case of (A1) the specific oxime compound.
As the (A2) biimidazole compound that can be used in the present invention, hexaarylbiimidazole is preferable, and lophine dimers described in JP-B Nos. 45-37377 and 44-86516, for example, 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′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (O-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.

  A biimidazole compound may be used individually by 1 type in a coloring curable composition of this invention, and may use 2 or more types together.

The total content of (A1) specific oxime compound and (A2) biimidazole in the colored curable composition of the present invention is 0.1 to 30% by mass in the total solid content of the colored curable composition. 25 mass% is more preferable, and 2-20 mass% is especially preferable.
The content ratio of (A) the specific oxime compound and (A2) biimidazole is preferably in the range of 90:10 to 50:50, and in the range of 90:10 to 65:35, in terms of mass. Is more preferable.

<Other polymerization initiators>
The colored curable composition of the present invention is a known polymerization other than the specific oxime compound and biimidazole compound represented by (A1) general formula (I) as the polymerization initiator as long as the effects of the present invention are not impaired. An initiator may be included.
In the colored curable composition of the present invention, the (A1) specific oxime compound and the (A2) other polymerization initiator that can be included together with the biimidazole compound are decomposed by light and start polymerization of the polymerizable compound described later. It is a compound that promotes and preferably has absorption in a wavelength region of 300 to 500 nm. Specifically, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid compounds, disulfones Examples include acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds having a structure different from that of the (A1) specific oxime compound. More specifically, for example, polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749 can be mentioned.
The content of the other polymerization initiator is preferably 30% by mass or less based on the total mass of (A) the specific oxime compound and (A2) biimidazole.

<(B) Polymerizable compound>
(B) The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, 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, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)
UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

  The photopolymerizable compound can be used in combination of two or more, in addition to being used alone. As content in the colored curable composition of a photopolymerizable compound, 3-55 parts are preferable with respect to 100 parts of total solid content in mass conversion, More preferably, it is 10-50 parts. (B) When the content of the polymerizable compound is within the above range, a sufficient curing reaction proceeds.

<(C) Colorant>
As the colorant that can be used in the colored curable composition of the present invention, various conventionally known inorganic pigments or organic pigments can be used. Further, a dye can be used if necessary.
Regardless of whether the pigment is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, considering the handling property, considering that it is preferable to have a high transmittance. Preferably, the pigment has an average primary particle size of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. When the particle diameter is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.

A transmission electron microscope is suitable for the measurement of the particle diameter of the pigment. For example, the total number of particles in the observation field at 30,000 to 100,000 times, the number of particles of the pigment exceeding 0.02 μm, and the number of pigment particles exceeding 0.08 μm. The particle size distribution can be grasped by measuring.
Regarding the primary particle size, the ratio of primary particles less than 0.02 μm and the ratio of primary particles exceeding 0.08 μm are obtained by observing the pigment powder with a transmission electron microscope, measuring the major axis of each primary particle, It can be obtained by calculating the ratio (number%) of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 30,000 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, and less than 0.02 μm and 0.08 μm are measured. The ratio of the primary particles exceeding is calculated. This operation is carried out for a total of three locations by changing the location of the pigment powder, and a value obtained by averaging the results is used.

Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.
Examples of the organic pigment, inorganic pigment, and metal oxide particle include pigments described in paragraph numbers [0030] to [0044] of JP-A-2008-224982, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the Cl substituent is changed to OH, and the like. Among these, pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242,
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, 58
C. I. Pigment Black 1, 7
Alternatively, titanium black [13M-C, 13R-N, Ako Kasei Co., Ltd. Tilack D manufactured by Mitsubishi Chemical Corporation] and the like can be mentioned.
Organic pigments can be used alone or in various combinations in order to increase color purity.

  In the present invention, as necessary, a fine and sized pigment can be used as the colorant (C). As the refined pigment, a so-called solvent salt milled pigment refined as a highly viscous liquid composition together with the pigment, the water-soluble organic solvent and the water-soluble inorganic salt is preferable.

In the present invention, when a dye is used as the colorant (A), a uniformly curable colored curable composition is obtained.
(A) There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

As content of (C) coloring agent in the colored curable composition of this invention, it is the range of 30 parts-70 parts with respect to 100 parts of total solids of this colored curable composition in mass conversion, The range of 35 parts to 55 parts is more preferable, and the range of 36 parts to 50 parts is more preferable. When the content of the colorant is within the above range, the effect of the present invention that suppresses discoloration due to heat appears remarkably, and even when the pigment concentration is high, the decrease in luminance due to heat is small, and the color concentration is sufficient and excellent. It is effective for ensuring color characteristics.
In the present invention, the “pigment concentration” refers to the mass% of the colorant relative to the total solid content of the colored curable composition.

  In the present invention, it is particularly desirable to use a pigment as a colorant, and to prepare a pigment dispersion composition in which a dispersant is previously added and dispersed in a solvent before preparing a colored curable composition. Further, before adjusting the pigment dispersion composition, it is preferable to refine the pigment through a salt milling process as described below, and in the pigment salt milling process or dispersion process, the pigment is coated with a polymer compound. It is preferable to use it. Even in a pigment made finer by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed and the pigment can be dispersed in the state of primary particles. When a pigment coated with a polymer compound is used, the dispersed primary particles are stably maintained, and a colored curable composition having excellent dispersion stability can be obtained.

  The coated pigment which is a preferred embodiment for the colorant (C) in the present invention is one in which the pigment is coated with a polymer compound. Here, the coating refers to a pigment refinement process (salt milling process). In the present invention, a new interface of a pigment having high surface activity, which is generated by miniaturization in the presence of a polymer compound such as a polymer dispersant, has a strong electrostatic action with the polymer compound useful for pigment dispersion. It is considered that a coating pigment having higher dispersion stability can be obtained by forming the coating layer. The coated pigment having a coating layer formed in such a miniaturization step hardly releases the coated polymer compound even when washed with an organic solvent that dissolves the polymer compound.

The salt milling process for forming the coated pigment will be specifically described. First, add a small amount of iii) a water-soluble organic solvent as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, knead strongly with a kneader, etc., and then throw this mixture into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
During salt milling, iii) by using a combination of iv) at least a partly soluble resin in the organic solvent, the pigment is agglomerated during drying, and the surface is further coated with iv) at least partly soluble resin. Can be obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling step, or may be added separately. It is also possible to add in the dispersion step.

The polymer compound used for coating the pigment is not particularly limited as long as it has an adsorbing group for the pigment, and is a polymer compound known as a pigment dispersant, particularly a polymer compound having a heterocyclic ring in the side chain. Is preferably used.
<(E) Pigment dispersant>
In the colored curable composition of this invention, when using a pigment as a coloring agent, it is preferable to use (E) pigment dispersant together.
As the pigment dispersant, a polymer compound having a heterocyclic ring in the side chain is preferable. Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
The alkyl group for R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.
Such compounds are described in detail in paragraph Nos. [0020] to [0047] of JP-A-2008-266627 (Effect FSP-10544), and the compounds described here are suitable as a pigment dispersant in the present invention. Can be used.
As the pigment dispersant, in addition to the above compounds, for example, known pigment dispersants and surfactants can be appropriately selected and used.

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

  (C) When using a pigment as a colorant, it is preferable from the viewpoint of improving the uniform dispersibility of the pigment that a pigment dispersion composition is first prepared and then added to the colored curable composition. In preparing the pigment dispersion composition, it is preferable to add 1 to 100 parts, and more preferably 3 to 70 parts, of these (E) pigment dispersants in terms of mass with respect to 100 parts of the pigment.

  A pigment derivative is added to the above-described pigment dispersion composition as necessary. A pigment derivative having an affinity for the dispersant or a polar group introduced is adsorbed on the pigment surface, and this is used as the adsorption point of the dispersant to disperse the pigment as fine particles in the pigment dispersion composition. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

  As content in the pigment dispersion composition of a pigment derivative, 1-30 parts are preferable with respect to 100 parts of pigments by mass conversion, and 3-20 parts are more preferable. When the content is within the above range, the viscosity can be kept low and the dispersion can be performed satisfactorily and the dispersion stability after the dispersion can be improved. When the color curable composition of the present invention is prepared by using a color filter to produce a color filter, a color filter having high contrast and good color characteristics can be obtained.

  As a dispersion method, for example, a pigment and, if necessary, a dispersant previously mixed in a solvent and premixed with a homogenizer or the like are finely dispersed using a bead disperser using zirconia beads or the like. You can do it.

<(D) Alkali-soluble binder resin having a double bond in the side chain>
The alkali-soluble resin functions as a binder component, but in the present invention, the alkali-soluble resin contains a specific alkali-soluble resin having a double bond in the side chain, so that the curability of the exposed portion is particularly improved. Both alkali developability of an unexposed part can be improved.

The alkali-soluble binder resin having a double bond in the side chain (D) used in the present invention has a structure in which the resin becomes alkali-soluble in order to improve various properties such as non-image area removability. And at least one unsaturated double bond. As a structure containing the unsaturated double bond, as a preferred specific embodiment, one having at least one selected from groups represented by the following partial structure (a) to partial structure (c) in the side chain is preferable. Can be mentioned. This resin, which is soluble in an alkaline aqueous solution and used as a binder resin for a negative image recording material, is at least one selected from groups represented by partial structures (a) to (c) in the side chain. If you have. Of course, you may have multiple types of such groups, and you may have all of these simultaneously.
Hereinafter, the side chains represented by the partial structure (a) to the partial structure (c) will be described.

In the partial structure (a) to the partial structure (c), R ^{4 to} R ⁶ , R ^{10 to} R ¹² , and R ^{16 to} R ²⁰ each independently represent a monovalent substituent. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents a hydrogen atom or a monovalent organic group. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents a hydrogen atom or a monovalent organic group.
The binder resin having such a partial structure is described in detail in JP-A No. 2003-262958, and the compounds described herein can be used in the present invention.

  The alkali-soluble binder resin having a double bond in the side chain (D) used in the colored curable composition of the present invention has an acid group in its structure in order to improve various performances such as non-image area removability. Have. The (D) alkali-soluble binder resin having a double bond in the side chain preferably contains a radical polymerizable compound having an acid group as a copolymer component.

  Examples of the acid group include carboxylic acid, sulfonic acid, phosphoric acid group, phenolic hydroxyl group, and the like, and particularly preferred is a carboxylic acid group. These may be used alone or in combination of one or more. The content of these copolymerization components used is preferably 5 to 50 mol%, particularly preferably from the viewpoint of suppressing image strength damage due to alkali water development. 10 to 40 mol%.

  Furthermore, the alkali-soluble binder resin having a double bond in the side chain (D) according to the present invention is used for the purpose of improving various performances such as image strength, as long as the effects of the present invention are not impaired. In addition to the radically polymerizable compound having a group, it is also a preferred embodiment that another radically polymerizable compound is further contained as a copolymer component.

  Examples of the radical polymerizable compound copolymerizable with the alkali-soluble binder resin having a double bond in the side chain (D) according to the present invention include acrylic acid esters, methacrylic acid esters, styrenes, acrylonitriles, methacrylates. Examples include radically polymerizable compounds selected from rhonitriles and the like.

  Among these radical polymerizable compounds, methacrylic acid esters, acrylamides, methacrylamides, and styrenes are preferably used.

  These may be used alone or in combination of two or more. ((D) In the alkali-soluble binder resin having a double bond in the side chain, the content of these copolymerization components used is preferably 0 to 90 mol%. Particularly preferably, the content is 0 to 60 mol%, and sufficient pattern formation can be obtained when the content is in the above range.

  Examples of the solvent used for synthesizing such a polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.

  Specific examples of such an alkali-soluble binder resin having a double bond in the side chain (D) include the following Exemplified Compound 1 to Exemplified Compound 31.

  (D) The acid value of the alkali-soluble binder resin having a double bond in the side chain can be calculated, for example, from the average content of acid groups in the resin molecule. Moreover, (D) Resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises the alkali-soluble binder resin which has a double bond in a side chain.

In the present invention, (D) the weight average molecular weight of the alkali-soluble binder resin having a double bond in the side chain is preferably 30,000 to 300,000 from the viewpoint of pattern peeling inhibition and developability during development. It is more preferably 35,000 to 250,000, further preferably 40,000 to 200,000, and particularly preferably 45,000 to 100,000.
In addition, the mass average molecular weight of (D) alkali-soluble binder resin which has a double bond in a side chain can be measured by GPC, for example.

  The content of the alkali-soluble binder resin having a double bond in the side chain (D) relative to the total solid content of the colored curable composition of the present invention is 0.1 to 7. Although 0 mass% is preferable, 0.3-6.0 mass% is more preferable from a viewpoint of coexistence of pattern peeling suppression and development residue suppression, and 1.0-5.0 mass% is further more preferable.

  Hereinafter, optional components that the colored curable composition may contain will be described.

<(E) Sensitizer>
The colored curable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes the above-mentioned (A1) specific oxime compound by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer 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.
That is, 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), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, 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, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

More preferable examples of the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
The content of the sensitizer is preferably in the range of 0.1 to 30% by mass, and in the range of 1 to 20% by mass, based on the total solid content of the colored curable composition, from the viewpoints of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

<(F) Co-sensitizer>
The colored curable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization of the photopolymerizable compound by oxygen.

  Examples of such co-sensitizers include amines such as MRSander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).

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

<(G) Binder polymer that may be used in combination>
In the colored curable composition, a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and are advantageous in terms of suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity and developability.

The weight average molecular weight of the binder polymer that can be used in the colored curable composition is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000. It is above, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing a binder polymer that can be used in the colored curable composition include known compounds such as an azo initiator and a peroxide initiator.

<(H) Polymerization inhibitor>
It is desirable to add a small amount of a polymerization inhibitor to the colored curable composition in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. As the polymerization inhibitor, known thermal polymerization inhibitors can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the colored curable composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

<(I) Adhesion improver>
An adhesion improver can be added to the colored curable composition in order to improve adhesion to a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.
Silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is preferable.
0.5-30 mass% is preferable in the total solid of a coloring curable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

<(J) Diluent>
In the colored curable composition, various organic solvents may be used as a diluent.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content with respect to the organic solvent is preferably 2 to 60% by mass.

<(K) Other additives>
Furthermore, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler, a plasticizer, or a sensitizer may be added to the colored curable composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

  The colored curable composition of the present invention comprises the above-described (A1) specific oxime compound, (A2) biimidazole compound, (B) polymerizable compound, (C) colorant (preferably a pigment dispersion containing a pigment dispersant). And (D) an alkali-soluble binder resin having a double bond in the side chain, optionally together with a solvent, and optionally mixed with an additive such as a surfactant. it can.

As described above, the colored curable composition of the present invention comprises (A1) a specific oxime compound and (A2) two photopolymerization initiators called a biimidazole compound and (D) an alkali-soluble resin binder resin having a double bond in the side chain. Therefore, it is cured with high sensitivity to form a high-definition colored pattern, and color unevenness of the colored pattern after post-baking is suppressed.
Such a colored curable composition is suitably used for various applications that require the formation of various high-definition and excellent color patterns, and is particularly required for high-definition and color unevenness control. It can be said that the effect is remarkable by using for the formation of the coloring pattern for filters.

<< Coloring Pattern Forming Method and Color Filter Having the Same >>
Next, the color pattern forming method of the present invention and the color filter having the color pattern obtained thereby will be described.
The colored pattern forming method of the present invention includes a step of forming a colored curable composition layer using the colored curable composition of the present invention,
A step of exposing and curing the colored curable composition layer in a pattern (hereinafter abbreviated as “colored photopolymerizable composition layer forming step” as appropriate), and the colored curable composition layer after the exposure. Developing and removing the uncured colored curable composition portion to form a colored pattern, and the step of forming the colored pattern is a step of pattern exposing the colored curable composition layer ( Hereinafter, abbreviated as “exposure step” as appropriate) and a step of developing the colored curable composition layer after exposure to form a colored pattern (hereinafter abbreviated as “development step” as appropriate). Including.
Moreover, the color filter of the present invention has a colored pattern formed on the support by the colored pattern forming method of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its production method (colored pattern forming method of the present invention).

Specifically, the colored curable composition of the present invention is applied directly or via another layer on a support (substrate) to form a colored curable composition layer (colored curable composition layer). Forming step), pattern exposure, preferably by exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developer (development step), coloring pattern Form. In the case of producing a color filter by this method, a color pattern of each color (3 colors or 4 colors) may be sequentially formed on a support to form pixels having a necessary hue. Further, as will be described later, the black matrix can also be formed from the colored curable composition of the present invention.
Hereinafter, each step will be described.

[Colored curable composition layer forming step]
In the colored curable composition layer forming step, the colored curable composition layer for a color filter of the present invention is applied on a support to form a colored curable composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
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.

  As a coating method of the colored curable composition for a color filter of the present invention on a support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like are applied. be able to.

The coating thickness of the colored curable composition is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.2 μm to 3 μm.
Moreover, when manufacturing the color filter for liquid crystal display elements, as a coating film thickness of the photopolymerizable composition for color filters, 0.1 micrometer-3.5 micrometers are preferable from a viewpoint of resolution and developability, 0 More preferably, the thickness is 5 μm to 2.0 μm.

  The photopolymerizable composition for a color filter coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a colored photopolymerizable composition layer.

[Exposure process]
In the exposure step, the colored photopolymerizable composition layer formed in the colored photopolymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, 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 seconds to 90 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. 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.

  In the method for forming a colored pattern of the present invention, after the above-described colored curable composition layer forming step, exposing step, and developing step are performed, the formed colored pattern is heated (post-baking) as necessary. And a curing step of curing by at least one means of exposure.

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.
The colored pattern formed by the colored curable composition of the present invention is highly precise and has no variation in hue because the occurrence of uneven color due to heating is suppressed even after this post-baking. A high intensity colored pattern is formed.

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

  Here, although the color filter of this invention was demonstrated centering on the aspect manufactured using the coloring pattern formation method of this invention, this invention is not limited to this aspect. For example, the colored curable composition layer forming step, the exposing step, and the developing step (and, if necessary, the curing step) in the forming method of the present invention are also applied when forming a black matrix on the substrate. Specifically, a black matrix (black pattern) is formed on the substrate by performing the above steps using the colored curable composition of the present invention containing a black colorant such as carbon black or titanium black. be able to.

  The color filter of the present invention comprises a colored pattern formed using the colored curable composition of the present invention, but the colored curable composition has excellent exposure sensitivity and good adhesion to the substrate of the exposed portion. It is possible to form a high-resolution pattern that provides a desired cross-sectional shape. Further, even when post-baking is performed to improve the curability of the colored pattern, the occurrence of color unevenness due to heat treatment is suppressed, so that it is suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD. Therefore, it is suitable for a liquid crystal display element that requires an excellent hue. That is, the color filter of the present invention is preferably applied to a liquid crystal display element.

<< Liquid crystal display element >>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display element of the present invention.
According to an aspect of the present invention, a colored curable composition that is excellent in image formability and suppresses occurrence of uneven color even after post-baking, a colored pattern forming method using the colored curable composition, and the colored pattern formation A color filter provided with the coloring pattern formed by the method can be provided. In particular, it is possible to provide a color filter with good pattern formation, less color unevenness and film defects, and high contrast. By using this color filter, a liquid crystal display element including high-quality colored pixels is provided. be able to.

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

[Synthesis Example 1: (A1) Specific Oxime Compound: Synthesis of Compound 1]
(A1) The specific oxime compound [Compound 1] was synthesized by the method shown below.
First, Compound A was synthesized according to the scheme shown below.
Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) was added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 ° C., and the reaction solution was added dropwise.
The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

Next, Compound 1 is synthesized using Compound A.
Compound A (20.0 g, 47.9 mmol) is dissolved in 64 ml of THF and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) are added. Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution and refluxed for 2 hours. Next, after cooling to 0 ° C., a 28% methanol solution of sodium methoxide (11.1 g, 57.4 mmol) is added dropwise over 20 minutes, and the mixture is warmed to room temperature and stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours.
The reaction solution is diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was filtered with suction and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain a solid (yield 17.0 g, yield 64%).
The solid (46.4 g, 85 mmol) was dissolved in 230 ml of ethyl acetate and triethylamine (10.3 g, 101 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (8.0 g, 102 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was washed with 1000 ml of distilled water cooled to 0 ° C. and extracted with ethyl acetate. After concentration under reduced pressure, the solution was added dropwise to 100 ml of distilled water, and the precipitated solid was subjected to suction filtration, washed with 150 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound 1 having the following structure (yield 49.7 g, yield 99%). )

Moreover, the structure of the obtained specific compound 1 was identified by NMR.
(1H-NMR 400 MHz CDCl3): 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d, 1H, J = 8.0 Hz), 7.51-7.24 (m.10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36 (s) , 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

  In Comparative Examples described later, (A1) Comparative Compound 1 (Irgacure OXE 01, manufactured by Ciba Specialty Chemicals Co., Ltd.), Comparative Compound 2 (Irgacure OXE 02), Comparative Compound 3 (Id, Irgacure) was used instead of the specific oxime compound. The structure of 369) is as follows.

[Example 1]
[1. Preparation of colored curable composition A-1]
As a colored curable composition, a negative-type colored curable composition A-1 containing a colorant (pigment) was prepared, and a color filter was produced using the negative colored curable composition A-1.

[Synthesis Example 2: Synthesis of Resin (i-1)]
6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).
The scheme is shown below.

[Synthesis Example 3: Synthesis of Resin (J-1)]
10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of polyester resin (i-1) are mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). It was. Thereafter, the mixture was allowed to cool to 65 ° C., 200 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Thereafter, PGMEA was added to obtain a 10 mass% PGMEA solution of the resin (J-1). Resin (J-1) has a side chain derived from polyester (i-1) and a carboxy group derived from succinic anhydride.
A synthesis scheme is shown below.

1-1. Preparation of pigment dispersion -Preparation of dispersion of yellow pigment PY150-
As a pigment, C.I. I. 40 parts (average particle diameter 60 nm) of Pigment Yellow 150 (PY150), 223 parts of PGMEA 10% by mass solution of the resin (J-1) (22.3 parts in terms of solid content) was mixed with a bead mill (zirconia beads 0. 3 mm) to mix and disperse for 3 hours to prepare a pigment dispersion.

-Preparation of dispersion of green pigment PG36-
As a pigment, C.I. I. A mixed liquid consisting of 40 parts of pigment green 36 (PG36) (average particle size 60 nm) and 200 parts of resin (i-1) (20 parts in terms of solid content) was mixed with a bead mill (zirconia beads 0.3 mm) for 3 hours. Dispersed to prepare a pigment dispersion. With respect to the pigment dispersion, the average primary particle diameter of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.

1-2. Preparation of colored curable composition A-1 (coating liquid) The components of the following composition A-1 were mixed and dissolved to prepare a colored curable composition A-1.

<Composition A-1>
(Composition 1)
-Dispersion of green pigment PG36 [(C) Colorant] 26.1 parts-Dispersion of yellow pigment PY150 [(C) Colorant] 14.3 parts-Benzyl methacrylate-methacrylic acid copolymer (copolymerization mole) 7: 3 ratio
Weight average molecular weight 5000, acid value: 113) [Combination alkali-soluble resin] 2.0 parts, Exemplified compound 21 [(D) Specific alkali-soluble resin] 0.9 part. 5 to 6 polymerizable groups in one molecule Polymeric monomer (Nippon Kayaku Co., Ltd. product name: KAYARAD DPHA, 7: 3 (mass ratio) mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [(B) polymerizable compound] 3.54 parts Compound 1 [(A1) specific oxime compound] 1.24 parts · 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole [(A2) imidazole compound] 57 parts-Compound having an epoxy ring (1,2-epoxy-4- (2-oxolanyl) of 2,2-bis (hydroxymethyl = 1-butanol) Cyclohexane adduct,
EHPE-3150 manufactured by Daicel Chemical Industries, Ltd. 0.480 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0018 parts ・ Surfactant (fluorine-based surfactant, trade name Megafac F781-F manufactured by DIC Corporation)
0.0334 parts ・ Silane coupling agent (3-methacryloyloxy-trimethoxysilylpropane)
0.320 parts Solvent (PGMEA) 51.42 parts

In addition, the conditions of the gel permeation chromatography method (GPC) measurement which calculates | requires a weight average molecular weight and a number average molecular weight are as follows.
Column used: TSKgel MultiporeHXL-M
(Porous polydisperse type linear column) manufactured by Tosoh Eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Tosoh HLC-8220)

[2. (Production of color filter)
2-1. Formation of colored curable composition layer After applying a slit on a glass substrate provided with a black matrix of 550 mm × 650 mm as a resist solution, the colored curable composition A-1 containing the pigment obtained as described above was applied under the following conditions: Vacuum drying (66 Pa) and pre-baking (80 ° C., 160 seconds) were performed to form a colored curable composition coating film (colored curable composition layer).

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

2-2. Exposure and development Subsequently, the colored curable composition layer was exposed in a pattern at 60 mJ / cm ² using a proximity exposure machine (manufactured by Hitachi High-Technology Corporation, LE5565A). The entire surface of the colored curable composition layer after exposure is showered with a 1.0% aqueous solution (25 ° C.) of an inorganic developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) at a shower pressure. The pressure was set to 0.2 MPa, development was performed for 60 seconds, and the plate was washed with pure water.

2-3. Heat treatment Then, pure water was sprayed onto the colored curable composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-bake). In this way, a green coloring pattern was formed on the substrate.

2-4. Formation of red and blue coloring patterns Thereafter, a coloring pattern is formed with a blue coloring curable composition (CB-9500L; manufactured by Fuji Film Electronics Materials Co., Ltd.), and further a red coloring curable composition (CR- 9500L; FUJIFILM Electronics Materials Co., Ltd.), a colored pattern is formed, ITO is deposited, and a photopolymerizable composition (CSP-3210L; FUJIFILM Electronics Materials Co., Ltd.) is used to form a spacer. A color filter having green, red, and blue coloring patterns (pixels) on the substrate was obtained.

[3. (Performance evaluation)
-Colored layer development process, colored layer baking (post-baking) process-
For the purpose of evaluating the colored pattern for the color filter, the same operation as in the above-described step 2-1 is performed to form a colored curable composition layer, and then using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) (1 part by weight of CDK-1 and 99 parts by weight of pure water, 25 ° C.) The shower pressure was set to 0.2 MPa, the development time was developed in 10 seconds to 10 seconds, washed with pure water to form a colored pattern, and the colored pattern of Example 1 was obtained. It was. Example 2 is the same as Example 1 except that the types and contents of the specific polymerization initiator, sensitizer, and co-sensitizer (A1) and (A2) are changed as shown in Table 1. -Color patterns of Example 9 and Comparative Examples 1 to 3 were formed.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 1 are the compounds shown below.

-Evaluation of development time-
The substrate with a development time of every 10 seconds was observed with an optical microscope, and the development status was evaluated. In Table 2, the lower limit of the development time is the lower limit number of seconds of usable development time, and the non-pixel portion cannot be removed in a time shorter than this time. The upper limit of the development time is the upper limit of the usable development time in seconds. If the time is longer than this time, the pixel is missing or dropped out. Moreover, 80 seconds or less are preferable from the restriction of the process (tact time). The development latitude indicates a difference in the number of seconds between the upper limit of the development time and the lower limit of the development time.

-Evaluation of pattern linearity-
An edge portion of the colored pattern was photographed and evaluated using an optical microscope (200 times in reflection mode). A pixel edge portion was observed in a 5 cm × 5 cm photograph and evaluated according to the following criteria.
“Good”: The pixel edge portion looks linear “Slightly good”: The pixel edge portion is partially non-linear (within 1/3 of the total length), but not jagged. “Slightly bad”: The pixel edge portion is not linear exceeding 1/3 of the entire length, or part (less than 1/4 of the entire length) is jagged “Bad”: Pixel edge part is more than 1/4 of the total length and is jagged

  The edge portion of the pixel pattern is preferably a linear shape. If the edge portion of the pixel pattern becomes jagged due to residual film, undercut, or the like, it is necessary to increase the overlap with the black matrix. In this case, the width of the black matrix is widened and the aperture ratio is lowered. Further, when the overlap with the black matrix is not increased, there is a possibility that a white portion without a colored layer is formed near the edge of the black matrix. Furthermore, when the edge portion of the pixel pattern is jagged, there is a problem that the transparent electrode formed thereon is disconnected and the resistance value is increased.

−Evaluation of bites−
The edge portion of the pixel pattern was photographed and evaluated using an optical microscope (200 times in reflection mode). A pixel edge portion was observed in a 5 cm × 5 cm photograph to determine the presence or absence of a chip.
Judgment criteria are (1) a shape in which the edge portion disappears in a half-moon shape, and (2) it may be longer than (1), but the line width becomes discontinuously narrower than the surroundings and is recognized as missing. When any one of the above was observed, it was evaluated as “×” as having a chip.
The case where the above-mentioned chipping was not seen at all was indicated as “◯”.
When chipping occurs, the portion is white and light is lost, which is not preferable.

-Evaluation of uneven color after post-baking-
Using a light microscope (200 times in the reflection mode), a picture of the pattern that reversed the pixel pattern was evaluated. Evaluation is based on the following criteria. In addition, the micrograph of the color unevenness used as the reference | standard of determination was image | photographed on the conditions of bright field observation with the magnification 1000 times with Olympus optical microscope MX51. It shows a photomicrograph as a reference of determination color unevenness under Symbol Figure 1. When it looks like FIG. 1 (A), it judged with "there is no color irregularity" and was set as "(circle)". As shown in FIG. 1B, when color shading is confirmed in the pattern, it is determined that “there is uneven color”. It was set as “x”.

  From Table 2, Examples 1 to 9 using the colored curable composition of the present invention exhibited good developability with large development latitude, good pattern linearity, and no occurrence of cracks in pattern formation. . Further, there was no color unevenness after post-baking.

(Example 10, Example 11)
Instead of Compound 1 in Example 1, (A1) The following Compound 2 and Compound 3 (synthesized in the same manner as in Synthesis Example 1 except that benzenethiol was changed to the corresponding compound) were used as specific oxime compounds, respectively. When the colored curable composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1, the same result as in Example 1 was obtained.

(Example 12)
In Example 1, the heat treatment conditions in the post-bake process were changed from 1 hour at a temperature of 220 ° C. to 1 hour at 160 ° C., the substrate was immersed in an N-methylpyrrolidone solution for 5 minutes (25 ° C.), and the obtained substrate When the sample was observed with an optical microscope in the same manner as the evaluation of chipping, it was observed that the surface was slightly rough.
(Example 13)
In Example 6, the heat treatment conditions in the post-bake process were changed from 1 hour to 160 ° C. for 1 hour at a temperature of 220 ° C., and the substrate was immersed in an N-methylpyrrolidone solution for 5 minutes (25 ° C.). The surface roughness was not observed when the sample was observed with an optical microscope in the same manner as the chip evaluation.
In contrast with Examples 12 and 13, when the content ratio of the (A1) specific oxime compound and the (A2) biimidazole compound is in a preferable range, the curability of the colored pattern is further improved and the development resistance is improved. I understand that

(Example 14)
11.5 parts of a dispersion liquid prepared in the same manner as in Example 1 except that the pigment type is replaced with 28.9 parts of the dispersion liquid of the green pigment PG36 using a purple pigment PV23 instead of the dispersion liquid of the yellow pigment PY150. In addition, as a polymerizable monomer having 5 to 6 polymerizable groups in one molecule, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) is used instead of KAYARAD DPHA. A color filter was prepared in the same manner as in Example 1 except that the composition was adjusted and the exposure process was changed to the following using this colored curable composition, and the same evaluation was performed. Good results similar to those of Example 1 were obtained.
(Exposure process)
Using EGIS (buoy technology Co., Ltd., YAG laser third harmonic wavelength 355 nm, pulse width 6 nsec) as a laser exposure device, pulse irradiation of about 1 mJ / cm ² was performed 20 times on the surface of the photosensitive resin composition layer. I went through a photomask.
From this result, it can be seen that even with pattern exposure using a laser exposure machine, the excellent effects of the present invention can be obtained as with exposure using a high-pressure mercury lamp.

(Comparative Example 4)
A color filter was prepared and evaluated by the same exposure process as in Example 14 using the colored curable composition of Comparative Example 1, and the same results were obtained except for the surface roughness of Comparative Example 1. . As for surface roughness, the surface roughness was worse than that of exposure with a mercury lamp as in Comparative Example 1.

Claims (5)

(A1) a compound represented by the following general formula (1), (A2) a biimidazole compound, (B) a polymerizable compound, (C) a colorant, and (D) an alkali-soluble binder having a double bond in the side chain A colored curable composition containing a resin.

In the general formula (I), R, B ⁰ and Q each independently represent a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, and n2 represents an integer of 0 to 5. .   The colored curable composition according to claim 1, wherein the (C) colorant is a pigment and further contains (E) a pigment dispersant. Forming a colored curable composition layer using the colored curable composition according to claim 1 or 2, and
Exposing and curing the colored curable composition layer in a pattern; and
Developing the colored curable composition layer after the exposure, removing an uncured colored curable composition portion, and forming a colored pattern;
A method for forming a colored pattern, comprising:   A color filter having a colored pattern formed on the support using the method according to claim 3.   A liquid crystal display device comprising the color filter according to claim 4.