KR20100115710A - Colored curable composition, method of forming colored pattern, color filter, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A coloring curable composition, method for forming coloring pattern, color filter and liquid crystal display with suppressed color ununiformity and wide development latitude are provided. CONSTITUTION: A coloring curable composition contains a compound of general formula 1, non-imidazole compound, polyerizable compound, coloring agent, and alkali soluble binder resin having double bond at the side chain. The coloring curable composition further contains pigment dispersing agent.

Description

Colored curable composition, formation method of colored pattern, color filter, and liquid crystal display device {COLORED CURABLE COMPOSITION, METHOD OF FORMING COLORED PATTERN, COLOR FILTER, AND LIQUID CRYSTAL DISPLAY DEVICE}

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

As a colored curable composition, what added the photoinitiator to the polymeric compound which has an ethylenically unsaturated bond, for example is used. Since such colored curable compositions are polymerized and cured by irradiation with light, they are used for photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.

In addition, coloring curable

 As the composition, for example, another form is known in which an acid is generated by irradiation with light and the generated acid is used as a catalyst. Specifically, semiconductor production, TFT production, and color filter using a color reaction of a dye precursor using an acid generated as a catalyst for image formation, anti-counterfeiting, energy dose detection, and a decomposition reaction using a generated acid as a catalyst It is used for positive resists, such as manufacture and micromachine parts manufacture.

In recent years, the coloring curable composition which has a sensitivity to the light source of short wavelength (365 nm or 405 nm) especially is calculated | required in various uses, The demand for the compound which shows the outstanding sensitivity with respect to such a short wavelength light source, for example, the photoinitiator, has become high. have. However, in general, the photoinitiator which is excellent in the sensitivity is lacking in stability, and the photoinitiator which satisfy | fills also stability with time-lapse stability is calculated | required.

Therefore, as a photoinitiator used for a colored curable composition, an oxime ester derivative is proposed by US Patent No. 4255513, US Patent 4490145, Japanese Unexamined-Japanese-Patent No. 2000-80068, and Japanese Unexamined-Japanese-Patent No. 2001-233842. It is. However, these well-known oxime ester derivatives have low absorbance with respect to wavelength 365nm and wavelength 405nm, and satisfaction was not yet acquired from a viewpoint of a sensitivity.

In addition, it is a present situation that it is required to be excellent in stability with time also as coloring curable composition, and to have the outstanding sensitivity with respect to light of short wavelength, such as 365 nm and 405 nm.

For example, Japanese Unexamined Patent Application Publication No. 2006-195425 discloses a colored radiation-sensitive composition for color filters containing an oxime compound of a specific structure, but with respect to stability over time and sensitivity to light of short wavelengths Was not enough yet. Moreover, in the color curable composition for color filters, the reproducibility of the color after pattern formation becomes a new subject, and the improvement of the problem that a coloring property changes with time is calculated | required strongly.

On the other hand, color filters for liquid crystal display devices have a strong demand for high color density of color filters in order to expand the color reproduction region. If a large amount of colorant is added in order to obtain a high coloring concentration, sensitivity tends to be insufficient, resulting in a large number of missing patterns. In addition, in order to eliminate this missing, higher energy light irradiation is required, so that the exposure time becomes longer and the yield on manufacturing becomes remarkable. As mentioned above, about the color curable composition for color filters, while containing a coloring agent in high concentration, favorable pattern formation property is calculated | required.

In the color filter manufacturing process, it is common to perform a post-heating process or a so-called post-baking process in order to improve the effectiveness when forming a colored pattern, but there is a problem that color unevenness occurs at the end of the pattern after heat treatment. It turned out.

The 1st objective of this invention is the coloring polymerizability which the linearity is favorable, the coloring pattern without missing is formed, the image development latitude at the time of pattern formation is wide, and the color nonuniformity of the coloring pattern by a postbaking process was suppressed. It is in providing a composition.

The 2nd object of this invention is to provide the formation method of the coloring pattern which has favorable pattern formation property, is wide development latitude, and was excellent in productivity.

Further, a third object of the present invention is to provide a color filter having no color unevenness, a color pattern having a high resolution and a good pattern shape, and a liquid crystal display device having the color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the present inventors solved the said subject by using the oxime compound of the specific structure, the biimidazole compound, and the binder resin of a specific structure. Specific means for solving the problems are shown below.

<1> (A1) Alkali-soluble binder which has a double bond in the compound represented by following General formula (1), (A2) biimidazole compound, (B) polymeric compound, (C) coloring agent, and (D) side chain Colored curable composition containing resin.

The formula (I) of the, R, B ^0, and Q each independently represents a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, n2 is an integer of 0 to 5.

The coloring curable composition of <2> <1> in which the said (C) coloring agent is a pigment and contains (E) pigment dispersant further.

The process of forming a colored curable composition layer using the colored curable composition as described in <3> <1> or <2>, the process of exposing and hardening the said colored curable composition layer in a pattern form, and the colored curable composition after the said exposure. The formation method of the coloring pattern which has a process of developing a layer and removing the uncured coloring curable composition part and forming a coloring pattern.

The color filter which has a coloring pattern formed on the <4> support body using the method as described in <3>.

The liquid crystal display device provided with the color filter as described in <5> <4>.

(Effects of the Invention)

According to the present invention, there is provided a colored polymerizable composition having good linearity, a colored pattern without missing defects, a wide development latitude during pattern formation, and suppressed color unevenness of the colored pattern by a postbaking step. do.

Moreover, according to this invention, the formation method of the coloring pattern which has favorable pattern formation property, is wide in development latitude, and excellent in productivity is provided.

Moreover, according to this invention, the color filter which has a color pattern without color nonuniformity, and has a high-resolution and favorable pattern shape, and the liquid crystal display device provided with the said color filter can be provided.

1 shows a micrograph serving as a reference for the color non-uniformity determination of a colored pattern produced using the colored polymerizable composition of the present invention, (A) is a determination example of “no color non-uniformity because there is no color in the pattern”, (B) is an example of determination that the light and shade of a color are recognized in a pattern, and "there is a color nonuniformity."

Hereinafter, the coloring curable composition of this invention, the formation method of the coloring pattern using the said colored curable composition, the color filter which has the said coloring pattern, the liquid crystal display device using the said color filter, and a solid-state image sensor are demonstrated in detail.

<< coloring curable composition >>

The colored curable composition of this invention is a compound represented by (A1) General formula (1) (Hereinafter, it may be called a specific oxime compound.), (A2) biimidazole compound, (B) polymeric compound, and (C) A coloring agent and (D) It is characterized by containing alkali-soluble binder resin which has a double bond in a side chain.

First, the colored curable composition of this invention is demonstrated.

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

In the general formula (I), R, B ^0, and Q each independently represents a monovalent organic group, Z represents a hydrogen atom or a monovalent substituent, n2 is an integer of 0 to 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 promotes polymerization of the (B) polymerizable compound described later. It has a function as a photoinitiator. In particular, since a specific oxime compound has the outstanding sensitivity to the light source of 365 nm or 405 nm, it exhibits the outstanding effect when it is used together with a polymeric compound in a colored curable composition as a photoinitiator.

The colored curable composition of this invention is able to form the cured film which has high sensitivity with respect to the light of wavelength 365nm and 405nm, is excellent in time-lapse stability, and can suppress coloring by heat-time-lapse. Although this detailed mechanism is unclear, since a specific oxime compound has a structure which absorbs light and suppresses radical recombination at the time of cleavage, a large amount of generated radicals can achieve high sensitivity. Moreover, since radical recombination is suppressed, it is thought that reaction with the decomposition products of a specific oxime compound is suppressed at the time of heating, and the coloring derived from the reaction is suppressed.

In addition, in this invention, in order to evaluate the coloring by the time course of heat of a cured film, you may use color difference ((DELTA) E ^* ab). Here, color difference ((DELTA) E ^* ab) can be measured with MCPD-3000 by Otsuka Denshi Corporation.

As conditions at the time of evaluation, first, the colored curable composition of this invention is exposed to various exposure doses of the range of 10mJ / cm <2> -2500mJ / cm <2> with an ultrahigh pressure mercury lamp proxy meter type | mold exposure machine or i-line stepper exposure apparatus (365nm), and a cured film is exposed. Form. And after image development develops as desired, a cured film is heated at 200 degreeC for 1 hour.

The coloring state by heating of a cured film can be evaluated by measuring the color difference ((DELTA) E ^* ab) before and behind this cured film's heating.

By using the colored curable composition of this invention, the color difference ((DELTA) E ^* ab) before and behind heating can be made into 3 or less, the coloring change by heating can be reduced significantly, and the color filter with high color purity can be obtained.

Although the specific oxime compound of this invention can be synthesize | combined by the method shown, for example in Unexamined-Japanese-Patent No. 2007-269778-0069, It is not limited to this method.

In the general formula (I), R represents a monovalent organic group.

As monovalent organic group represented by R in General formula (I), the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, and a substituent Alkylsulfinyl group which may have, arylsulfinyl group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, Aryloxycarbonyl group which may have a substituent, phosphinoyl group which may have a substituent, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, and di which may have a substituent And alkylaminocarbonyl groups and dialkylaminothiocarbonyl groups which may have a substituent. It may have a good acyl groups are preferred.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable and a methyl group, an ethyl group, a propyl group, etc. are mentioned, for example.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable, For example, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group etc. are mentioned.

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.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable, for example, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

As an alkyl sulfinyl group which may have a substituent, a C1-C20 alkyl sulfinyl group is preferable, For example, a methyl sulfinyl group, an ethyl sulfinyl group, a propyl sulfinyl group, etc. are mentioned.

As an aryl sulfinyl group which may have a substituent, a C6-C30 aryl sulfinyl group is preferable, For example, a phenyl sulfinyl group, 1-naphthyl sulfinyl group, 2-naphthyl sulfinyl group, etc. are mentioned.

As an alkylsulfonyl group which may have a substituent, a C1-C20 alkylsulfonyl group is preferable, For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. are mentioned.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, For example, a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, etc. are mentioned.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, For example, an 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-chlorobenzo diary, 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 group, etc. are mentioned.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, For example, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group , An octadecyloxycarbonyl group, a trifluoromethyloxycarbonyl group, etc. are mentioned.

Examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group and the like.

As the phosphinoyl group which may have a substituent, a phosphinoyl group having 2 to 50 carbon atoms is preferable, and for example, dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimetho A oxy phosphinoyl group, a diethoxy phosphinoyl group, a dibenzoyl phosphinoyl group, a bis (2, 4, 6- trimethylphenyl) phosphinoyl group, etc. are mentioned.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocyclic group containing a hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a person atom is preferable. Examples of the heterocyclic group include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a cromenyl group, A xanthenyl group, a phenoxatinyyl group, etc. are mentioned.

Examples of the alkylthiocarbonyl group which may have a substituent include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, trifluoromethylthiocarbonyl group and the like. Can be mentioned.

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, and 4-methylsulfanylphenylthiocarbonyl group.

Examples of the dialkylaminocarbonyl group which may have a substituent include dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, and the like.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include dimethylaminothiocarbonyl group, dipropylaminothiocarbonyl group, dibutylaminothiocarbonyl group and the like.

Among these, as a monovalent organic group represented by R, an acyl group is more preferable at the point of high sensitivity, and an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are specifically preferable.

As a specific example of the monovalent organic group represented by R in the said General formula (I), what is shown below is preferable from a viewpoint of high sensitivity.

In the general formula (I), as the monovalent organic group represented by B ⁰ , a phenyl group which may have a substituent, a C1-C20 alkyl group which may have a substituent, a C1-C20 alkenyl group which may have a substituent, A C1-C20 alkynyl group which may have a substituent, a C5-C8 cycloalkyl group which may have a substituent, a C2-C20 alkanoyl group which may have a substituent, a benzoyl group which may have a substituent, and a substituent optionally it may have an alkoxycarbonyl group, a substituent having a carbon number of 2 to 12 have a good good phenoxy carbonyl group, -S (O) mR ¹² (only, R ¹² represents an alkyl group having a carbon number of 1~6, m is an integer from 0 to 2 .), -S (O) mR ¹³ (wherein R ¹³ represents an aryl group having 6 to 12 carbon atoms and may be substituted with an alkyl group having 1 to 12 carbon atoms, and m is an integer of 0-2.), The substituent Tan which you may have Number which may have an alkoxy sulfonyl group, the substituents of 1 to 6 can be cited an aryloxy group or a fabric treatment diphenylphosphino group of 6 to 10 carbon atoms good.

In the formula (I), when B ⁰ represents a phenyl group, introduction of possible substituent the alkyl group, a phenyl group, a halogen atom, -OR ^8, -SR ⁹ or -N (R ¹⁰⁾ having a carbon number of 1~6 (R ¹¹⁾ These may be mentioned and you may have two or more these substituents.

In addition, when B <^0> represents a C2-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a C2-C11 alkoxycarbonyl group, one among the carbon atoms which comprise a principal chain It may have the above oxygen atom or S atom 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 ). You may have two or more of these.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 6 carbon atoms substituted with a substituent, provided that the substituent is a hydroxy group, mercapto group, cyano group, alkoxyl group having 1 to 4 carbon atoms, and alkenes having 3 to 6 carbon atoms. Nyloxy group, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group of 4 to 7 carbon atoms, alkylcarbonyloxy group of 2 to 5 carbon atoms, phenylcarbonyloxy group, carboxyl group or 2 to 5 carbon atoms Or an alkoxycarbonyl group.], An alkyl group having 2 to 6 carbon atoms having at least one oxygen atom between carbon atoms constituting the main chain, an alkanoyl group having 2 to 8 carbon atoms, and-(CH ₂ CH ₂ O) nH (Wherein 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 1 carbon atom) may be substituted with an alkoxy group to 4 in.), a phenyl alkyl group having a carbon number of _{^{7~9, -Si (R 14) r}} (R 15) 3-r ( However, R ¹⁴ is Represents an alkyl group of a small number of 1~8, R ¹⁵ is a phenyl group, r is an integer from 1 to 3) are shown.

R ⁹ to R ¹¹ are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, an alkyl group having 2 to 6 carbon atoms substituted (wherein the substituent is a hydroxy group, mercapto group, or cyano group). Alkoxyl 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, alkylcarbonyl jade having 2 to 5 carbon atoms Or at least one of a phenylcarbonyloxy group, a carboxyl group or an alkoxycarbonyl group having 2 to 5 carbon atoms.}, 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, it may be substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms), and a phenylalkyl group having 7 to 9 carbon atoms.

In general formula (I), although Z represents a hydrogen atom or a monovalent substituent, As a monovalent substituent represented by Z, For example, Halogen groups, such as a fluorine atom; Alkoxy groups such as methoxy group, ethoxy group and 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 an acetyl group and a benzoyl group; Alkylsulfanyl groups such as methylsulfanyl group; Aryl sulfanyl groups, such as a phenyl sulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; In addition to aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group, hydroxy group, carboxyl 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, trimethyl ammonium group, dimethyl sulfonyl group, triphenylphenacyl phosphonine Push, cyano group, etc. are mentioned.

As a monovalent substituent represented by Z of general formula (I), an alkoxy group, an alkylamino group, an arylamino group, an alkyl group, and an aryl group are preferable.

As Z in general formula (I), a hydrogen atom or said monovalent substituent is preferable.

n2 represents the integer of 0-5, 0-3 are preferable and 0 or 1 is more preferable.

When n2 represents the integer of 2-5, Z may be the same substituent or may be another substituent.

The example of the structure represented by the following general formula (I-1) except the oxime ester structure in the compound represented by said general formula (I) is shown below.

Although the specific example of a compound represented by general formula (I) is shown below, it is not limited to these.

The compound represented by the said general formula (I) is 12,000-500,000 in molar extinction coefficient in 365 nm. As for the specific example shown below, all have the molar extinction coefficient in the range of 12,000-500,000.

The oxime polymerization initiator represented by the general formula (I) has a maximum absorption wavelength in a region around 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, and may use 2 or more types together for a colored curable composition.

As content in the colored curable composition of (A1) specific oxime compound, 0.1 part-8.0 parts are preferable with respect to 100 parts of total solids of the said colored curable composition by mass conversion from a viewpoint of sclerosis | hardenability and coloring property, More preferably, it is 0.5 part- 6.0 parts.

<(A2) Biimidazole Compound>

The colored curable composition of this invention needs to contain the (A2) biimidazole compound further. The biimidazole compound (A2) is a compound having a function of decomposing by exposure in a region having a wavelength of 300 nm to 500 nm and producing and advancing the polymerization of the polymerizable compound described later, similarly to the specific oxime compound (A1).

As (A2) biimidazole compound which can be used for this invention, hexaaryl biimidazole is preferable, and the poppin dimers described in Unexamined-Japanese-Patent No. 45-37377 and Unexamined-Japanese-Patent No. 44-86516, for example 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, etc. are mentioned. have.

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

The total content of the (A1) specific oxime compound and (A2) biimidazole in the colored curable composition of the present invention is 0.1 to 30% by mass of the total solids of the colored curable composition, more preferably 1 to 25% by mass, 2-20 mass% is especially preferable.

Moreover, it is preferable that it is the range of 90: 10-50: 50 in mass conversion, and, as for the content rate of (A) specific oxime compound and (A2) biimidazole, it is more preferable that it is the range of 90: 10-65: 35. .

<Other polymerization initiators>

The colored curable composition of this invention contains well-known polymerization initiators other than the specific oxime compound and biimidazole compound represented by (A1) general formula (I) as said polymerization initiator in the range which does not impair the effect of this invention. You may also

In the colored curable composition of the present invention, the other polymerization initiator which may be contained together with the (A1) specific oxime compound and the (A2) biimidazole compound is decomposed by light and initiates and promotes polymerization of the polymerizable compound described later. It is a compound to make it, and it is preferable to have absorption in the area | region of wavelength 300-500 nm. Specifically, for example, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound, a metallocene compound, an organic boric acid compound, A disulfonic acid compound and the oxime ester compound, an onium salt compound, and the acyl phosphine (oxide) compound which differ in structure from the said (A1) specific oxime compound are mentioned. More specifically, the polymerization initiator as described in Paragraph Nos. [0081]-[0100], [0101]-[0139] etc. of Unexamined-Japanese-Patent No. 2006-78749 is mentioned, for example.

It is preferable that content of another polymerization initiator is 30 mass% or less with respect to the total mass of (A) specific oxime compound and (A2) biimidazole.

<(B) polymeric compound>

As the (B) polymerizable compound, a compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 ° C. or higher at atmospheric pressure is preferable.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group and whose boiling point is 100 degreeC or more at normal pressure, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl ( Monofunctional acrylates and methacrylates such as methacrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japan Urethane acrylates described in Japanese Patent Application Laid-open No. 50-6034, Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 48-64183, and Japanese Patent Polyfunctional acrylates and methacrylates, such as the polyester acrylates of Unexamined-Japanese-Patent No. 49-43191, Japanese Unexamined-Japanese-Patent No. 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Can be mentioned.

Moreover, the thing introduce | transduced as a photocurable monomer and an oligomer can also be used by Japanese adhesion association vol.20, No. 7, pages 300-308.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 with the specific examples as General Formulas (1) and (2), (meth) acrylated Compounds can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

Moreover, urethane acrylates and the Japanese patent publications described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. Hei 2-16765. Also preferred are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, Japanese Patent Publication 56-17654, Japanese Patent Publication 62-39417, and Japanese Patent Publication 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 It is possible to obtain a photopolymerizable composition having excellent photosensitive speed. As a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku pulp company), UA-7200 "(made by Shin-nakamura Chemical Co. Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoiisha), etc. are mentioned.

Moreover, ethylenically unsaturated compounds which have an acid group are also preferable, As a commercial item, it is TO-756 which is carboxyl group-containing trifunctional acrylate made by Toagosei Co., Ltd., and TO-1382 which is carboxyl group-containing 5-functional acrylate, for example. Etc. can be mentioned.

As the polymerizable compound used in the present invention, a tetrafunctional or higher acrylate compound is more preferable.

A photopolymerizable compound can be used in combination of 2 or more type other than using individually by 1 type. As content in the colored curable composition of a photopolymerizable compound, 3-55 parts are preferable with respect to 100 parts of total solids in mass conversion, More preferably, it is 10-50 parts. Sufficient hardening reaction advances in content of (B) polymeric compound in the said range.

<(C) Colorant>

As a coloring agent which can be used for the colored curable composition of this invention, the conventionally well-known various inorganic pigment or organic pigment can be used. Moreover, dyes can also be used as needed.

Considering that the pigment is preferably high transmittance irrespective of the inorganic pigment or the organic pigment, it is preferable to use a pigment having a small particle size and a small particle size as far as possible, and considering the handling property, it is preferable that the average primary The particle diameter is 0.01 µm to 0.3 µm, more preferably 0.01 µm to 0.15 µm. When the particle diameter is in the above range, the transmittance is high, the color characteristics are good, and it is effective to form a high contrast color filter.

A transmission electron microscope is preferable for the measurement of the particle diameter of a pigment, for example, particle size distribution by measuring the total particle number in the observation visual field at 30,000 to 100,000 times, and the particle number of the pigment exceeding 0.02 μm and more than 0.08 μm. Can be identified.

The ratio of the primary particles of less than 0.02 μm to the primary particle size, and the ratio of the primary particles of more than 0.08 μm were measured by measuring the long diameter of each primary particle by observing the pigment powder with a transmission electron microscope, and measuring 0.02 It can obtain by calculating the ratio (number%) of the particle | grains of a pigment less than micrometer and exceeding 0.08 micrometer. More specifically, the pigment powder was observed at 30,000 to 100,000 times with a transmission electron microscope, the photograph was taken to measure the long diameter of 1000 primary particles, and the ratio of primary particles smaller than 0.02 μm and larger than 0.08 μm. To calculate. This operation is performed about three places in total by changing the site | part of a pigment powder, and the value which averaged the result is used.

Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and The complex oxide of the said metal is mentioned.

As said organic pigment, an inorganic pigment, and a metal oxide particle, the pigment of Unexamined-Japanese-Patent No. 2008-224982 Paragraph No. [0030]-[0044], the Cl substituent of CIPigment Green 58 and CIPigment Blue 79 are mentioned, for example. The thing which changed to OH, etc. are mentioned, Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it 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

Or titanium black [13M-C, 13R-N, Ako Kasei Co., Ltd. Tilack D by Mitsubishi Kagaku Co., Ltd.] etc. are mentioned as a commercial item.

An organic pigment can be used individually or in combination in order to raise color purity.

In this invention, the pigment finely refined and can be used as (C) coloring agent as needed. As the micronized pigment, a so-called sorbent salt milling pigment micronized as a high viscosity liquid composition together with a pigment, a water-soluble organic solvent and a water-soluble inorganic salt is preferable.

In this invention, when using dye as a (A) coloring agent, the colored curable composition melt | dissolved uniformly 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 Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, US Patent No. 4,808,501, US Patent 5,667,920, US Patent 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115 Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open 8-62416, Japanese Patent Publication 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Publication Hei 8-302224 The pigment | dye of Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. are mentioned.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pyrrolo. Dyestuffs, such as a pyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, can be used.

As content of the (C) coloring agent in the colored curable composition of this invention, it is the range of 30-70 parts with respect to 100 parts of total solids of the said colored curable composition by mass conversion, and the range of 35-55 parts is more preferable, 36 The range of part-50 parts is more preferable. When the content of the colorant is within the above range, the effect of the present invention, in which discoloration due to heat is suppressed, is remarkable, and the luminance decrease due to heat is small even at the concentration of the raw material, and the color concentration is sufficient, which is effective for securing excellent color characteristics.

In addition, in this invention, "pigment concentration" means the mass% of the coloring agent with respect to the total solid of a colored curable composition.

In this invention, it is especially preferable to use the pigment as a coloring agent, and to make it into the pigment dispersion composition which added the dispersing agent etc. in advance and disperse | distributed in the solvent, before adjusting a colored curable composition. Moreover, before adjusting a pigment dispersion composition, it is preferable to refine | miniaturize a pigment through the salt milling process mentioned later, and it is preferable to use what coat | covered the pigment with a high molecular compound in the salt milling process or dispersion process of a pigment. By coating the pigment with a high molecular compound, the formation of secondary aggregates can be suppressed even in the finely pigmented pigment, which can be dispersed in the state of primary particles. When the pigment coated with a high molecular compound is used, the dispersed primary particles are stably maintained to obtain a colored curable composition having excellent dispersion stability.

Although the coating pigment which is a preferable form for the coloring agent (C) in this invention is what coat | covered the pigment with a high molecular compound, in this case, coating | covering is refine | miniaturized by coexisting high molecular compounds, such as a polymeric dispersing agent, in the refinement | miniaturization process of a pigment (salt milling process). The new interface of the pigment with high surface activity resulting from the formation of the pigment indicates a strong coating layer of the polymer compound by a strong electrostatic action with the polymer compound useful for pigment dispersion, and the coating layer is formed to have a coating pigment having higher dispersion stability. It is thought that is obtained. Even if the coating pigment which has the coating layer formed in such a refinement | miniaturization process wash | cleans with the organic solvent which melt | dissolves a high molecular compound, the coated high molecular compound is hardly liberated.

The salt milling process for forming the coating pigment will be specifically described. First, a small amount of iii) water-soluble organic solvent is added to the mixture of i) organic pigment and ii) water-soluble inorganic salt as a humectant and kneaded vigorously with a kneader or the like, and then the mixture is poured into water and stirred with a high speed mixer or the like to give a slurry. Let's do it. Next, this slurry is filtered, washed with water and dried as necessary to obtain a finely pigmented pigment. In addition, when disperse | distributing to an oily varnish and using it, it is also possible to disperse | distribute the process pigment (called a filtration cake) before drying to oily varnish, removing water by the method generally called flashing. Moreover, when disperse | distributing to an aqueous varnish, a process pigment does not need to be dried, and a filter cake can be disperse | distributed to a varnish as it is.

The use of iv) at least a part of soluble resin in combination with the iii) organic solvent at the time of salt milling results in a finer surface, and iv) at least a small amount of aggregation of the pigment at the time of coating drying with at least part of the soluble resin.

In addition, the timing of adding a iv) polymer compound may be added all at the beginning of a salt milling process, and may be added separately. Moreover, it can also add in a dispersion process.

The polymer compound to be used for coating the pigment can be used without particular limitation as long as it has an adsorptive group to the pigment, and it is preferable to use a known polymer compound, particularly a polymer compound having a heterocycle in the side chain, as the pigment dispersant.

<(E) Pigment Dispersant>

When using a pigment as a coloring agent in the colored curable composition of this invention, it is preferable to use (E) pigment dispersant together.

As the pigment dispersant, a high molecular compound having a heterocycle in the side chain is preferable. As such a high molecular compound, it is preferable that it is a polymer containing the monomer represented by following General formula (1), or the polymer unit derived from the monomer which consists of a maleimide and a maleimide derivative, and is represented by following General formula (1) It is especially preferable that it is a polymer containing the polymerization unit derived from.

In said 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 (= 0) O-, -CONH-, -OC (= 0)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.

As an alkyl group of R <^1> , a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ¹ has a substituent, as the substituent, for example, a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), and a methoxy group , Ethoxy group, cyclohexyloxy group and the like.

About such a compound, it is described in detail in Unexamined-Japanese-Patent No. 2008-266627 (Patent FSP-10544) Paragraph No. [0020]-[0047], The compound described here can be used suitably as a pigment dispersant in this invention. have.

As a pigment dispersant, a well-known pigment dispersant and surfactant can be used suitably, besides the said compound, for example.

Specifically, most kinds of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. Cationic surfactants such as .90, No. 95 (manufactured by Kyoeisha Kagaku Kogyo Co., Ltd.), and W001 (manufactured by Yusho Corporation); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Chiba Specialty Chemical Co., Ltd.), Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Polymer dispersants such as Disperse Aid 9100 (all manufactured by Sanofko Corp.); Various Solsper dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) And Isonet S-20 (manufactured by 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, and 2150 (manufactured by Big Chemie Co., Ltd.). In addition, the oligomer or polymer which has a polar group in a molecular terminal or a side chain, such as an acryl-type copolymer, is mentioned.

(C) When using a pigment as a coloring agent, it is preferable to prepare a pigment dispersion composition first, and to add to a colored curable composition after that from a viewpoint of the uniform dispersion tendency of a pigment. In preparing a pigment dispersion composition, it is preferable to add 1-100 parts of these (E) pigment dispersants in mass conversion with respect to 100 parts of pigments, and it is more preferable to add 3-70 parts.

In the pigment dispersion composition described above, a pigment derivative is added as necessary. By adsorbing a pigment derivative having affinity to the dispersant or a polar group introduced thereon onto the surface of the pigment and using this as the adsorption point of the dispersant, the pigment can be dispersed as fine particles in the pigment dispersion composition to prevent reaggregation. It is effective in forming 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 in mass conversion, and 3-20 parts are more preferable. If the said content is in the said range, while disperse | distributing can be performed favorably while suppressing a viscosity low, the dispersion stability after dispersion can be improved, high transmittance | permeability and the outstanding color characteristic are obtained, and it uses the coloring curable composition of this invention. When a color filter is manufactured by adjusting the color filter, a color filter having high contrast and good color characteristics can be obtained.

The method of dispersion can be performed by undispersing a pigment and the dispersing agent previously in a solvent as needed, and previously mixing with a homogenizer etc. using the bead disperser etc. which used zirconia beads etc., for example.

<(D) Alkali-soluble binder resin having a double bond in the side chain>

Although alkali-soluble resin functions as a binder component, in this invention, both the hardening of an exposure part and the alkali developability of an unexposed part can be improved especially by containing specific alkali-soluble resin which has a double bond in a side chain as alkali-soluble resin.

Alkali-soluble binder resin having a double bond in the (D) side chain used in the present invention is an acid group and at least one unsaturated double bond for the resin to be alkali-soluble in order to improve various performances such as non-image removal property in the structure. Has As a structure containing this unsaturated double bond, what has at least 1 sort (s) chosen from the group represented by the following partial structure (a)-partial structure (c) in a side chain as a preferable specific aspect is mentioned. This resin soluble in alkaline aqueous solution and used as a binder resin of a negative image recording material may have at least one selected from the group represented by partial structures (a) to (c) in the side chain. Naturally, you may have two or more types of these groups, and may have all these at the same time.

Hereinafter, the side chain represented by partial structure (a)-partial structure (c) is demonstrated.

In the partial structures (a) to (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.

Binder resin which has such a partial structure is described in detail in Unexamined-Japanese-Patent No. 2003-262958, The compound described here can also be used for this invention.

Alkali-soluble binder resin which has a double bond in the (D) side chain used by the colored curable composition of this invention has an acidic radical in the structure, in order to improve various performances, such as a non-image part removal property. It is preferable that the alkali-soluble binder resin which has a double bond in the said (D) side chain contains the radically polymerizable compound which has an acidic radical as a copolymer component.

As said acid group, a carboxylic acid, a sulfonic acid, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxylic acid group is especially preferable. These can be used 1 type or 1 type or more, Preferably content of these copolymerization components is 5-50 mol%, Especially preferably, it is 10-40 mol% from the viewpoint of the image intensity damage suppression by alkaline-water image development.

Moreover, the alkali-soluble binder resin which has a double bond in the (D) side chain which concerns on this invention is a radical which has a specific functional group mentioned above, unless the effect of this invention is impaired for the purpose of improving various performances, such as image intensity | strength. In addition to a polymeric compound, it is also a preferable aspect to contain another radically polymerizable compound as a copolymer component.

As a radically polymerizable compound copolymerizable with the alkali-soluble binder resin which has a double bond in (D) side chain which concerns on this invention, acrylic acid ester, methacrylic acid ester, styrene, acrylonitrile, methacryl And radical polymerizable compounds selected from ronitriles and the like.

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

1 type, or 2 or more types can be used and (D) The content of these copolymerization components in alkali-soluble binder resin which has a double bond in a side chain preferably is 0-90 mol%, Especially preferably, it is 0-60 mol %to be. Sufficient pattern formation in content is obtained in the said range.

As a solvent used when synthesizing such a high molecular compound, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, acetic acid Ethyl, methyl lactate, ethyl lactate, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof.

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

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

The mass average molecular weight of the alkali-soluble binder resin having a double bond in the (D) side chain in the present invention is preferably from 30,000 to 300,000, more preferably from 35,000 to 250,000 from the viewpoint of suppression of pattern peeling at the time of development and developability. It is more preferable that it is 40,000-200,000, and it is especially preferable that it is 45,000-100,000.

In addition, the mass mean molecular weight of alkali-soluble binder resin which has a double bond in (D) side chain can be measured by GPC, for example.

Although content of alkali-soluble binder resin which has a double bond in the (D) side chain with respect to the total solid of the colored curable composition of this invention is 0.1-7.0 mass% in terms of polymerizability and alkali developability, but suppresses pattern peeling and image development residue 0.3-6.0 mass% is more preferable from a viewpoint of compatibility of suppression, and 1.0-5.0 mass% is still more preferable.

Hereinafter, the arbitrary components which a colored curable composition can contain are demonstrated.

<(E) sensitizer>

The colored curable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and lengthening the photosensitive wavelength.

As a sensitizer which can be used for this invention, it is preferable to sensitize the said (A1) specific oxime compound with 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 those having an absorption wavelength in the wavelength range 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 (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine) Merocyanines (e.g. merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. Crinidine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinones), squaryliums (e.g., squarylium), acridine oranges, coumarins (e.g., 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylme , Triphenylmethane, distyrylbenzene, carbazole, porphyrin, spiro compound, quinacridone, indigo, styryl, pyryllium compound, pyrromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid Aromatic ketone compounds, such as a derivative, a thiobarbituric acid derivative, acetophenone, benzophenone, a thioxanthone, Michler's ketone, heterocyclic compounds, such as N-aryl oxazolidinone, etc. are mentioned.

As a more preferable example of a sensitizer, the compound of Paragraph No. 0085-0098 of Unexamined-Japanese-Patent No. 2008-214395 is mentioned.

As for content of a sensitizer, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a colored curable composition from a viewpoint of a sensitivity and storage stability, The range of 1-20 mass% is more preferable, 2-15 mass% The range of is more preferable.

<(F) Notary sensitizer>

It is also preferable that the colored curable composition of this invention contains a sensitizer. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the active radiation, or inhibiting the polymerization inhibition of the photopolymerizable compound by oxygen.

Examples of such a desensitizer include amines such as MRSander et al., Journal of Polymer Society, Volume 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, The compound described in Research Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides, for example, a thiol compound disclosed in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, Japan The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto- 4 (3H) -quinazolin, (beta) -mercaptonaphthalene, etc. are mentioned.

As another example, an amino acid compound (e.g., N-phenylglycine, etc.), an organometallic compound (e.g., tributyltin acetate, etc.) described in JP-A-48-42965, JP-A-55-34414 is described. Hydrogen donors, sulfur compounds described in Japanese Patent Application Laid-open No. Hei 6-308727 (eg, trithiane) and the like.

As for content of a sensitizer, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the cure rate by the balance of a polymerization growth rate and a chain transfer, and the range of 1-25 mass% is More preferably, the range of 0.5-20 mass% is more preferable.

<(G) binder polymer which is good to use together>

In the colored curable composition, a binder polymer may be further used as necessary for the purpose of improving the coating properties. It is preferable to use linear organic polymer as a binder. As such a "linear organic polymer", a well-known thing can be used arbitrarily. Preferably, a linear organic polymer is selected that is soluble or swellable in water or weakly alkaline water in order to enable water development or weakly alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also as a water, weak alkaline water or an organic solvent developer. For example, the use of a water-soluble organic polymer enables water development. As such a linear organic polymer, a radical polymer having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication 54 -25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048, that is, a resin or an acid obtained by copolymerizing a monomer having a carboxyl group alone or in an acid; Resins obtained by hydrolyzing or half-esterifying or half-amidating an monomer having anhydride alone or copolymerizing, an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, and the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, and examples of the monomer having an acid anhydride include maleic anhydride.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group is useful.

When using alkali-soluble resin as a copolymer, you may use monomer other than the monomer mentioned above as a compound to copolymerize.

Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication The urethane-based binder polymers containing acid groups described in Japanese Patent Application Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. 1-271741, Japanese Patent Application Laid-open No. Hei 10-116232, and the like have excellent strength and are advantageous in terms of low exposure aptitude.

In addition, an acetal modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open No. 2001-318463, etc. is preferable because of excellent balance between film strength and developability. Moreover, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as water-soluble linear organic polymer. Moreover, alcohol-soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane and epichlorohydrin etc. are also useful in order to raise the intensity | strength of a hardened film.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomer if necessary] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable as needed Vinyl monomer] The copolymer is preferred because of its excellent balance between film strength, sensitivity and developability.

As a weight average molecular weight of the binder polymer which can be used by a colored curable composition, Preferably it is 5,000 or more, More preferably, it is the range of 10,000-300,000, About a number average molecular weight, Preferably it is 1,000 or more, More preferably, 2,000 It is the range of -250,000. As for polydispersity (weight average molecular weight / number average molecular weight), 1 or more is preferable, More preferably, it is the range of 1.1-10.

These binder polymers may be any of random polymers, block polymers and graft polymers.

The binder polymer which can be used by this invention can be synthesize | combined by a conventionally well-known method. As a solvent used at the time of synthesis | combination, tetrahydrofuran, ethylene dichloride, cyclohexanone, etc. are mentioned, for example. These solvents are used individually or in mixture of 2 or more types.

As a radical polymerization initiator used when synthesize | combining the binder polymer which can be used in a colored curable composition, well-known compounds, such as an azo initiator and a peroxide initiator, are mentioned.

<(H) polymerization inhibitor>

It is preferable to add a small amount of polymerization inhibitor to a colored curable composition in order to prevent unnecessary thermal polymerization of a polymeric compound during manufacture or storage of the said composition. As a polymerization inhibitor, a well-known thermal polymerization inhibitor can be used, Specifically, hydroquinone, p-methoxyphenol, di-t-butyl- p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4'-thiobis (3-methyl-6-t-butylphenol), 2,2'- methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt Etc. can be mentioned.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 to about 5 mass% is preferable with respect to the total solid of a colored curable composition.

Furthermore, in order to prevent the inhibition of polymerization by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added, and may be localized on the surface of the coating film in the drying process after coating. The amount of the higher fatty acid derivative added is preferably about 0.5 to about 10 mass% of the total composition.

<(I) Adhesion Enhancer>

In order to improve adhesiveness with hard surfaces, such as a support body, an adhesive improving agent can be added to a colored curable composition. As an adhesion promoter, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mer Captopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, and phenyl trimethoxysilane are preferable, and (gamma) -methacryloxypropyl trimethoxysilane is mentioned preferably.

0.5-30 mass% is preferable in the total solid of a colored curable composition, and, as for the addition amount of an adhesion promoter, 0.7-20 mass% is more preferable.

<(J) diluent>

You may use various organic solvents for a colored curable composition as a diluent.

As an organic solvent used here, 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 , Methoxy methoxy ethanol, 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 , And the like 3-methoxypropyl acetate, N, N- dimethylformamide, dimethyl sulfoxide, γ- lactone -butyrolactone, methyl lactate.

These solvents can be used individually or in mixture. It is preferable that the density | concentration of solid content with respect to the organic solvent is 2-60 mass%.

<(K) Other additives>

About a colored curable composition, in order to improve the physical property of a cured film, you may further add well-known additives, such as an inorganic filler, a plasticizer, a sensing agent.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and the like. When used, 10 mass% or less can be added with respect to the total mass of a polymeric compound and binder polymer.

The colored curable composition of the present invention comprises the above-mentioned (A1) specific oxime compound, (A2) biimidazole compound, (B) polymerizable compound, (C) colorant (preferably as a pigment dispersion composition containing a pigment dispersant), And (D) Alkali-soluble binder resin which has a double bond in a side chain can be contained with a solvent as needed, and additives, such as surfactant, can be mixed and prepared as needed for this.

As mentioned above, since the colored curable composition of this invention contains two types of photoinitiators, (A1) specific oxime compound, (A2) biimidazole compound, and (D) alkali-soluble resin binder resin which has a double bond in a side chain, It hardens | cures with high sensitivity, forms a highly precise coloring pattern, and suppresses generation | occurrence | production of the color nonuniformity of the coloring pattern after postbaking.

Such colored curable compositions are suitably used in various applications requiring the formation of various high precision and excellent color patterns, and in particular, the color curable compositions are used for the formation of color patterns for color filters requiring high precision and suppression of color unevenness. It is remarkable.

<< forming method of colored pattern and color filter having same >>

Next, the formation method of the coloring pattern of this invention and the color filter which has the coloring pattern obtained by it are demonstrated.

The coloring pattern formation method of this invention is a process of forming a colored curable composition layer using the colored curable composition of the said invention,

The step of exposing and curing the colored curable composition layer in a pattern form (hereinafter abbreviated to appropriately the "colored photopolymerizable composition layer forming step") and the colored curable composition layer after the exposure are developed and the uncured colored curable composition The process of removing a part and forming a coloring pattern has a process of pattern-exposing the said colored curable composition layer (henceforth abbreviated as "exposure process" suitably.), And the said coloring after exposure. It includes the step of developing the curable composition layer to form a colored pattern (hereinafter abbreviated to "development step" as appropriate).

Moreover, the color filter of this invention has a coloring pattern formed on the support body by the coloring pattern formation method of the said invention, It is characterized by the above-mentioned.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method (coloring pattern formation method of this invention).

Specifically, the colored curable composition of the present invention is applied onto the support (substrate) directly or through another layer to form a colored curable composition layer (color curable composition layer forming step), pattern exposure, preferably a predetermined mask. It exposes through a pattern, hardens only the coating film part irradiated with light (exposure process), and develops with a developing solution (development process), and forms a coloring pattern. When producing a color filter by this method, what is necessary is just to form the coloring pattern of each color (three colors or four colors) on a support body sequentially, and to form the pixel of a required color. Moreover, as mentioned later, a black matrix can also be formed with the colored curable composition of this invention.

Hereinafter, each process is demonstrated.

[Color curable composition layer forming step]

In the coloring curable composition layer forming process, the coloring curable composition for color filters of this invention is apply | coated on a support body, and a coloring curable composition layer is formed.

As a support body which can be used for this process, the soda glass used for a liquid crystal display element etc., Pyrex (trademark) glass, quartz glass, and the thing which adhered the transparent conductive film to these, or the photoelectric conversion element substrate used for an imaging element etc. For example, a silicon substrate, a complementary metal oxide film semiconductor (CMOS), etc. are mentioned. These board | substrates may be provided with the black stripe which isolate | separates each pixel.

In addition, on these supports, an undercoat layer may be formed as necessary to improve adhesion to the upper layer, to prevent diffusion of materials, or to planarize the surface of the substrate.

As a coating method of the color curable composition for color filters of this invention on a support body, various coating methods, such as a slit application | coating, an inkjet method, a rotary application | coating, cast | coating application | coating, roll coating, and screen printing, can be applied.

As coating film thickness of a colored curable composition, 0.1 micrometer-10 micrometers are preferable, 0.2 micrometer-5 micrometers are more preferable, 0.2 micrometer-3 micrometers are still more preferable.

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, and 0.5 micrometer-2.0 micrometers are more preferable.

The photopolymerizable composition for color filters applied on the support is usually dried at 70 ° C to 110 ° C under conditions of about 2 minutes to 4 minutes to form a colored photopolymerizable composition layer.

[Exposure process]

In an exposure process, the coloring photopolymerizable composition layer formed in the said coloring photopolymerizable composition layer formation process is exposed through a mask, and only the coating film part irradiated with light was hardened.

It is preferable to perform exposure by irradiation of radiation, and as radiation which can be used in exposure, especially ultraviolet rays, such as g line | wire, h line | wire, and i line | wire, are used preferably, and a high pressure mercury lamp is more preferable. 5mJ / cm <2> -1500mJ / cm <2> is preferable, 10mJ / cm <2> -1000mJ / cm <2> of irradiation intensity is more preferable, and 10mJ / cm <2> -800mJ / cm <2> is the most preferable.

[Developing process]

An alkali development process (development process) is performed following an exposure process, and the tailings irradiation part in an exposure process is eluted to aqueous alkali solution. This leaves only the photocured portion.

As a developing solution, the organic alkali developing solution which does not cause damage to a circuit of an underlayer etc. is preferable. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 second-90 second.

As an alkali used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- An alkaline aqueous solution in which organic alkaline compounds such as diazabicyclo- [5, 4, 0] -7-undecene is diluted 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 addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes (rinses) with pure water after image development.

Moreover, in the formation method of the coloring pattern of this invention, after performing the above-mentioned colored curable composition layer formation process, exposure process, and image development process, the coloring pattern formed as needed is heated (postbaking) and at least 1 means of exposure. You may include the hardening process to harden | cure by.

Post-baking is the post-development heat processing for making hardening perfect, and a thermosetting process of 100 degreeC-240 degreeC is normally performed. When a board | substrate is a glass substrate or a silicon substrate, 200 degreeC-240 degreeC is preferable also in the said temperature range.

This post-baking process can be performed continuously or batch type using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be in said condition.

Moreover, since the generation | occurrence | production of the color nonuniformity resulting from a heating is suppressed even if this coloring pattern formed by the coloring curable composition of this invention is post-baked, the high-strength colored pattern which does not have nonuniformity in color is formed.

The color filter which consists of a desired color is produced by repeating the coloring photopolymerizable composition layer formation process, exposure process, and image development process (and also the hardening process as needed) by the desired number of colors which were demonstrated above.

Here, although the color filter of this invention was demonstrated centering on the form manufactured using the coloring pattern formation method of this invention, this invention is not limited to this form. For example, the colored curable composition layer forming process, exposure process, and image development process (and the hardening process as needed) in the formation method of this invention are applied also when forming the black matrix on a board | substrate. Specifically, a black matrix (black pattern) can be formed on a board | substrate by performing each said process using the coloring curable composition of this invention containing black coloring agents, such as carbon black and titanium black.

Although the color filter of this invention is equipped with the coloring pattern formed using the coloring curable composition of this invention, a colored curable composition is excellent in exposure sensitivity, is good in adhesiveness with the board | substrate of an exposure part, and gives a desired cross-sectional shape. High resolution patterns can be formed. Moreover, even when postbaking is performed and the curability of a coloring pattern is improved, generation | occurrence | production of the color nonuniformity resulting from heat processing is suppressed, Therefore, it can be used suitably for solid-state image sensors, such as a liquid crystal display element and CCD, and excellent color is requested | required. It is suitable for the liquid crystal display element etc. which are used. That is, it is preferable that the color filter of this invention is applied to a liquid crystal display element.

<< liquid crystal display element >>

The liquid crystal display element of this invention comprises the color filter of this invention.

More specifically, an alignment film is formed on the inner surface side of the color filter, and the panel, which is the liquid crystal display element of the present invention, is obtained by opposing the electrode substrate so as to fill and seal the liquid crystal in the gap portion.

According to the aspect of this invention, the coloring curable composition which is excellent in image formation property, and generation | occurrence | production of a color nonuniformity is suppressed after postbaking, the coloring pattern formation method using the said colored curable composition, and the coloring pattern formation method formed by the said coloring pattern formation method A color filter having a pattern can be provided. In particular, it is possible to provide a color filter having good pattern formability, little color unevenness and film defects, and high contrast. By using this color filter, a liquid crystal display device having high-quality colored pixels can be provided.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the acclaim is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

Synthesis Example 1 (A1) Specific Oxime Compound: Synthesis of Compound 1

(A1) The specific oxime compound [Compound 1] was synthesize | combined by the method shown below.

First, compound A was synthesize | combined with the scheme shown below.

Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and cooled to 0 ° C., followed by addition of aluminum chloride (70.3 g, 0.527 mol). Then, o-tolyl chloride (81.5g, 0.527mol) was dripped over 40 minutes, it heated up to room temperature and stirred for 3 hours. Next, after cooling to 0 degreeC, aluminum chloride (75.1g, 0.563mol) was added. 4-chlorobutyl chloride (79.4 g, 0.563 mol) was dripped over 40 minutes, it heated up to room temperature and stirred for 3 hours. The mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 degreeC, and the reaction solution was dripped.

The precipitated solid was filtered off with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (amount 164.4 g, yield 77%).

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 the mixture is refluxed for 2 hours. Next, after cooling to 0 ° C, a 28% methanol solution of sodium methoxide (11.1 g, 57.4 mmol) was added dropwise over 20 minutes, and the temperature was raised to room temperature, followed by stirring for 2 hours. Next, after cooling to 0 degreeC, nitrous acid isopentyl (6.73 g, 57.4 mmol) is dripped over 20 minutes, it warms up to room temperature, and it stirred for 3 hours.

The reaction solution is diluted in 120 ml of acetone and added dropwise to 0.1N aqueous hydrochloric acid solution cooled to 0 ° C. The precipitated solid was washed with distilled water after suction filtration. Then, it recrystallized with acetonitrile and obtained the solid (amount 17.0g, 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 degreeC, acetyl chloride (8.0 g, 102 mmol) was dripped over 20 minutes, Then, it heated up 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 mixture was added dropwise to 100 ml of distilled water, and the precipitated solid was filtered off with suction, washed with 150 ml of isopropyl alcohol cooled to 0 ° C, and dried, and then Compound 1 (amount 49.7 g, yield 99%) having the following structure was dried. Got it.

In addition, the structure of the obtained specific compound 1 was identified by NMR.

(1H-NMR 400MHz 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 the comparative example mentioned later, (A1) Comparative compound 1 (Ciga specialty Chemicals make, monocure OXE 01) used instead of the specific oxime compound, comparative compound 2 (copper, monocure OXE 02), comparative compound 3 (copper, The structure of the monocure 369) is as follows.

Example 1

[1.Preparation of colored curable composition A-1]

The negative type colored curable composition A-1 containing a coloring agent (pigment) was prepared as a colored curable composition, and the color filter was produced using this.

Synthesis Example 2 Synthesis of Resin (i-1)

6.4 g of n-octanoic acid, 200 g of epsilon -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) were mixed, and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Then, it cooled to 65 degreeC, 200g of propylene glycol monomethyl ether acetate containing 3.8g of succinic anhydride (henceforth PGMEA) was added slowly, and it stirred for 2 hours. Then, PGMEA was added and the 10 mass% solution of PGMEA of resin (J-1) was obtained. Resin (J-1) has a side chain derived from polyester (i-1), and a carboxyl group derived from succinic anhydride.

The synthetic scheme is shown below.

1-1.Preparation of pigment dispersion

Preparation of Dispersion of Yellow Pigment PY150-

40 parts (average particle diameter 60nm) of CI pigment yellow 150 (PY150) as a pigment, and 223 parts (22.3 parts of solid content conversion) of PGMEA solution of the said resin (J-1) were mixed with the bead mill (zirconia beads 0.3) mm) was mixed and dispersed for 3 hours to prepare a pigment dispersion.

Preparation of Dispersion of Green Pigment PG36-

As a pigment, the mixture liquid which consists of 40 parts of CI pigment green 36 (PG36) (average particle diameter 60nm), and 200 parts of resin (i-1) (20 parts of solid content conversion) by bead mill (zirconia beads 0.3mm) for 3 hours. The pigment dispersion liquid was prepared by mixing and dispersing. It was 25 nm when the average primary particle diameter of the pigment was measured about the pigment dispersion liquid using the dynamic light-scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikki Corporation)).

1-2.Preparation of colored curable composition A-1 (coating solution)

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]... Part 26.1

· Dispersion of yellow pigment PY150 [(C) colorant]... Part 14.3

Benzyl methacrylate-methacrylic acid copolymer (copolymerization molar ratio 7: 3, weight average molecular weight 5000, acid value: 113) [combined alkali-soluble resin]... Part 2.0

Example Compound 21 [(D) Specific Alkali Soluble Resin]. 0.9 part

A polymerizable monomer having 5 to 6 polymerizable groups in one molecule (a 7: 3 (mass ratio) mixture of Nippon Kayaku Co., Ltd. brand name: KAYARAD DPHA, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) ((B) Polymeric compound]… 3.54 parts

Compound 1 [(A1) specific oxime compound]... Part 1.24

2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole [(A2) imidazole compound]... 0.57part

Compound having an epoxy ring (2,2-bis (hydroxymethyl = 1-butanol 1,2-epoxy-4- (2-oxoranyl) cyclohexane adduct, EHPE-3150 manufactured by Daicel Kagaku Corporation) … 0.480 parts

Polymerization inhibitor (p-methoxyphenol)... 0.0018part

Surfactant (fluorine-based surfactant, DIC Corporation brand name Megapack F781-F)... 0.0334parts

Silane coupling agent (3-methacryloxy-trimethoxysilylpropane)... 0.320part

Solvent (PGMEA). Part 51.42

In addition, the conditions of the gel permeation chromatography method (GPC) measurement which calculate | require the weight average molecular weight and a number average molecular weight are the following.

Use column: TSKgel MultiporeHXL-M (porous polydisperse linear column)

Eluent: THF

Flow rate: 1.0 ml / min

Temperature: 40 degrees Celsius

Detection condition: RI

System: High speed GPC device set (Tosho HLC-8220)

[2.Production of color filter]

2-1.Formation of colored curable composition layer

After slit-coating the colored curable composition A-1 containing the pigment obtained by making it into the resist solution on the glass substrate which formed the black matrix of 550 mm x 650 mm on the following conditions, vacuum drying (66 Pa) and prebaking (80 degreeC) 160 seconds) was performed to form a colored curable composition coating film (color curable composition layer).

(Slit application condition)

Gap between the opening of the coating head tip: 100 μm

Dispense rate: 150mm / second

Clearance of substrate and coating head: 150 μm

Coating thickness (dry thickness): 2 micrometers

Coating temperature: 23 degrees Celsius

2-2 Exposure, phenomenon

Thereafter, the colored curable composition layer was exposed in a pattern form at 60 mJ / cm 2 using a proxy meter exposure machine (manufactured by Hitachi High-Technologies Corporation, LE5565A). On the whole surface of the colored curable composition layer after exposure, 1.0% aqueous solution (25 degreeC) of an inorganic type developing solution (brand name: CDK-1, Fujifilm Electronics Co., Ltd. product) is set to shower pressure 0.2MPa by shower pressure, It developed for 60 second and wash | cleaned with pure water.

2-3.Heat Treatment

Thereafter, pure water was sprayed onto the colored curable composition layer in a shower to wash off the developer, and then heated in an oven at 220 ° C. for 1 hour (postbaking). In this way, the green coloring pattern was formed on the board | substrate.

2-4.Formation of red and blue coloring patterns

Thereafter, a colored pattern is formed with a blue colored curable composition (CB-9500L; manufactured by Fujifilm Electronics), and a red colored curable composition (CR-9500L; Fujifilm Electronics) is manufactured. )) To form a colored pattern, and evaporate ITO to form a spacer using a photopolymerizable composition (CSP-3210L; manufactured by Fujifilm Electronics), and to form green, red, and blue on the substrate. The color filter which has a coloring pattern (pixel) of was obtained.

[3. Performance evaluation]

Colored layer developing process, colored layer baking (post-baking) process

For the purpose of evaluating the color pattern for color filters, the same operation is carried out to the above-mentioned step 2-1 to form a colored curable composition layer, and then using a developing device (manufactured by Hitachi Hi-Tech Co., Ltd.), potassium hydroxide developer CDK- The shower pressure is set to 0.2 MPa with 1.0% developer (1 part by mass of CDK-1, 99 parts by mass of pure water diluted at 25 ° C) of 1 (manufactured by FUJIFILM Materials) Was developed at 10 second intervals between 10 seconds and 110 seconds, washed with pure water to form a colored pattern to obtain the colored pattern of Example 1. In addition, except having changed the kind and content of the specific polymerization initiator, sensitizer, and co-sensitizer of (A1) and (A2) as Table 1, it carried out similarly to Example 1, and was carried out similarly to Example 2-Example 9, and a comparative example. The coloring pattern of 1-the comparative example 3 was formed.

The sensitizers A1-A3 and co-sensitizers F1-F3 shown in Table 1 are compounds shown below.

Evaluation of development time

Every 10 seconds of development time, the board | substrate was observed with the optical microscope, the condition of image development was evaluated, and it put together in Table 2 and shown. In Table 2, the developing time lower limit is the lower number of seconds of usable development time, and the non-pixel portion cannot be removed at a time shorter than this time. The developing time upper limit is the upper limit number of seconds of usable development time, and in a time longer than this time, missing or dropping occurs in the pixel. Moreover, 80 second or less is preferable from a process (tact time) constraint. In addition, the developing latitude has shown the difference of the number of seconds between the upper limit of the developing time and the lower limit of the developing time.

Evaluation of pattern linearity

The edge part of a coloring pattern was photographed and evaluated using the optical microscope (200 times in reflection mode). The pixel edge part was observed in the 5 cm x 5 cm photograph, and the following references | standards evaluated.

`` Good '': The pixel edge part looks straight

`` Slightly good '': the pixel edge part is not straight (some 1/3 or less of full length) is not straight, but is not

"Slightly bad": Pixel edge part is more than one-third of the total length and is not linear, or part (a quarter or less of full-length) is kneaded

"Bad": Pixel edge part exceeds 1/4 of full length, and is knurled

It is said that the linear shape of the edge part of a pixel pattern is preferable. If the edge portion of the pixel pattern is jagged due to residual film, undercut, or the like, it is necessary to increase the overlap with the black matrix, and in that case, increase the width of the black matrix to lower the aperture ratio. In addition, when the overlap with the black matrix is not large, there is a possibility that a portion that is whited out without a colored layer may occur near the edge of the black matrix. In addition, when the edge portion of the pixel pattern is jagged, there is a problem such that the transparent electrode formed thereon is disconnected to increase the resistance value.

Evaluation of the missing

The edge part of a pixel pattern was photographed and evaluated using the optical microscope (200 times in reflection mode). The pixel edge part was observed in the 5 cm x 5 cm photograph, and the presence or absence of the absence was determined.

The criterion of determination is that (1) half-moon-shaped edge part disappears and (2) (1) is thinner and longer than it is, but it is recognized that the line width is discontinuously thinner than the surroundings and is missing. In the case of a missing case, it evaluated as "B".

It was set as "A" that the above-mentioned deletion | missing was not seen at all.

If a fallout occurs, the part is unfavorable because the light falls out white.

Evaluation of Color Unevenness after Post Baking

The photograph of the pattern inverted from a pixel pattern was evaluated using the optical microscope (200 times in a reflection mode). Evaluation is based on the following criteria. In addition, the microscopic picture of the color nonuniformity used as the reference | standard of determination is image | photographed under the conditions of bright field observation by 1000 times magnification with Olympus optical microscope MX51. The micrograph used as the reference | standard of a color nonuniformity determination is shown in following FIG. When it looked like FIG. 1 (A), it determined with "there is no color nonuniformity" and set it as "A". As shown in Fig. 1 (B), when the color tone is confirmed in the pattern, it is determined that there is color unevenness and is set to "B".

From Table 2, Examples 1-9 using the colored curable composition of this invention showed large developing latitude in pattern formation, the linearity of a pattern was also favorable, and showed the favorable developability without the occurrence of a deletion. Moreover, there was no color irregularity after postbaking.

(Example 10, Example 11)

Instead of compound 1 in Example 1, the following compound 2 and compound 3 (each synthesized in the same manner as in Synthesis Example 1 were synthesized by changing the benzene thiol to the corresponding compound) as the specific oxime compound (A1). In the same manner as in Example 1, the colored curable composition was adjusted, and evaluation was performed in the same manner as in Example 1, whereby the same results as in Example 1 were obtained.

(Example 12)

In Example 1, the heat treatment conditions of the post-baking process were changed from 1 hour to 160 degreeC 1 hour at the temperature of 220 degreeC, the board | substrate was immersed in N-methylpyrrolidone solution for 5 minutes (25 degreeC), and the board | substrate obtained In the same manner as in the absence evaluation, the optical microscope observed a slight roughness of the surface.

(Example 13)

In Example 6, the heat treatment conditions of the post-baking process were changed from 1 hour at 160 degreeC to 1 hour at 160 degreeC, the board | substrate was immersed in N-methylpyrrolidone solution for 5 minutes (25 degreeC), and the board | substrate obtained The surface roughness was not observed as a result of observing the optical microscope in the same manner as in the absence evaluation.

In contrast with Examples 12 and 13, it is understood that the content ratio of the (A1) specific oxime compound and the (A2) biimidazole compound is in a preferable range. have.

(Example 14)

11.5 parts of a dispersion liquid, which was adjusted in the same manner as the pigment species by using purple pigment PV23 instead of the yellow pigment PY150, was used in 28.9 parts of the dispersion liquid of the green pigment PG36, which was used in Example 1, and the polymerizable group was contained in one molecule. Instead of KAYARAD DPHA as a polymerizable monomer having 5 to 6, NK ester A-TMMT (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.) was used to adjust the colored curable composition, and the exposure step was performed using the colored curable composition. A color filter was produced in the same manner as in Example 1 except that the color filter was changed to the same as that of Example 1, and the same evaluations were carried out. As a result, the same good results as in Example 1 were obtained.

(Exposure process)

Pulse irradiation of about 1 mJ / cm <2> was performed through the photomask 20 times with respect to the surface of the photosensitive resin composition layer using EGIS (V Technology, 3rd harmonic wavelength of 355 nm, pulse width 6 nsec) as a laser exposure apparatus. .

From this result, it turns out that the outstanding effect of this invention is acquired similarly to the exposure by a high pressure mercury lamp also by the pattern exposure by a laser exposure machine.

(Comparative Example 4)

Using the colored curable composition of Comparative Example 1, a color filter was produced by the same exposure process as in Example 14 and evaluated, and the same result was obtained except for the surface roughness of Comparative Example 1. In addition, about the surface roughness, the state of surface roughness was worse than the exposure by a mercury lamp like Comparative Example 1.

Claims (5)

(A1) Contains the compound represented by following General formula (1), (A2) biimidazole compound, (B) polymeric compound, (C) coloring agent, and (D) alkali-soluble binder resin which has a double bond in a side chain. The colored curable composition characterized by the above-mentioned.

[In 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 method of claim 1,
The said (C) coloring agent is a pigment, and further contains the (E) pigment dispersant, The colored curable composition characterized by the above-mentioned. Process of forming colored curable composition layer using the colored curable composition of Claim 1 or 2;
Exposing and curing the colored curable composition layer in a pattern; And
And developing the colored curable composition layer after the exposure, and removing a portion of the uncured colored curable composition to form a colored pattern. It has a coloring pattern formed on the support body using the formation method of the coloring pattern of Claim 3, The color filter characterized by the above-mentioned. The color filter of Claim 4 is provided, The liquid crystal display device characterized by the above-mentioned.

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