JP2010061041A - Radiation-sensitive composition, color filter, black matrix, and liquid crystal display element - Google Patents

Abstract

に代表される特定の（Ｄ）光重合開始剤を含有する。
【選択図】なしIt is possible to form a fine pattern without causing chipping or undercut of a pattern edge even at a low exposure amount, and without remaining undissolved material or scum at the pattern edge during development. To provide a radiation-sensitive composition for forming a colored layer capable of forming a color filter having a high purity and a black matrix having a high light-shielding property.
The radiation-sensitive composition comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and the following compound Nos. 1

The specific (D) photoinitiator represented by is contained.
[Selection figure] None

Description

  The present invention relates to a radiation-sensitive composition, a color filter, a black matrix, and a liquid crystal display element for forming a colored layer used in a color liquid crystal display device, an imaging tube element and the like. More specifically, a colored layer-forming radiation-sensitive composition that can easily produce a colored layer excellent in various properties such as coating film properties and has excellent developability, and a colored layer formed from the composition. The present invention relates to a color filter having a black matrix comprising a color filter and a colored layer formed from the composition, and a liquid crystal display device including the color filter or the black matrix.

Conventionally, when forming a color filter or a black matrix using a radiation-sensitive composition, the radiation-sensitive composition is applied to the substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and the solvent is removed. A colored layer that is a pixel array or a black matrix of each color is obtained by exposing and developing the obtained coating film in a desired pattern. The colored layer formed in this manner is liable to cause residues and background stains on the unexposed substrate or the light shielding layer during development, and to the colored layer substrate or the light shielding layer formed in the exposed portion. In addition, there was a problem that the color layer which was post-baked after development was inferior in physical properties of the coating film.
Patent Document 1 includes (1) a photopolymerization initiator, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) a copolymer of styrene or a nucleus-substituted derivative thereof and maleic anhydride. A photopolymerizable composition containing an alkali-soluble resin obtained by reacting with an aralkylamine compound having a primary amino group has alkali solubility, and has excellent developer resistance, alkali resistance, substrate adhesion, etc. It is disclosed that a filter can be formed. However, in recent years, there has been a demand for a radiation-sensitive composition capable of forming a color filter with high color purity and a black matrix with high light-shielding properties, and therefore it is necessary to increase the pigment concentration in the composition. . As a result, a residue is more likely to remain during the development of the composition, and there is a problem that adhesion between the substrate and the colored layer is insufficient, and a solution is desired.
Furthermore, in recent years, in the technical field of color filters, it has become mainstream to reduce the exposure amount and shorten the tact time, coupled with the increase in the size of the substrate used to form the color filters. It is required that the pixel and the black matrix formed in a quantity are excellent in pattern shape, adhesion to the substrate, and the like. However, in the conventionally known colored radiation-sensitive compositions, if the exposure amount decreases, the pattern is likely to be chipped or undercut, or the pattern is not easily adhered to the substrate, and thus the pattern is likely to peel off from the substrate. It was difficult to obtain pixels and a black matrix having a good pattern shape while shortening the tact time.
A radiation-sensitive composition that can form a color filter with high color purity and a black matrix with high light-shielding properties without causing such problems has not been known.

By the way, in the exposure process as described above, it is general to use ultraviolet light called “Type 1” which has fairly strong emission lines in the vicinity of 300 nm, 315 nm and 340 nm in addition to the light having the wavelength of 365 nm which shows the maximum intensity. It is. However, if light having a strong emission line in a wavelength region of 340 nm or less with high energy is used, the exposure machine is easily damaged and is not preferable. Therefore, “Type 2” and “Type 3” which suppress the intensity of these short-wavelength lights are used. The use of a so-called light source is preferred, and the use of a light source called “Type 4” that does not include light of these short wavelengths tends to be preferred. However, it has been clarified that the radiation sensitivity is insufficient when a conventionally known radiation-sensitive composition is applied to a light source of Type 2 to Type 4.
Therefore, there is a need for a radiation-sensitive composition that exhibits high radiation sensitivity even when Type 2 to Type 4 which is kind to an exposure machine is used as a light source.
Japanese Patent Laid-Open No. 7-110577 Japanese Patent Laid-Open No. 9-71733 JP-A-9-95625 JP-A-9-124969

The present invention has been made in view of the above circumstances, and its purpose is to use a radiation-sensitive composition for forming a colored layer exhibiting excellent developability, more specifically, a light source with a short wavelength cut. Fine pattern formation without chipping and undercutting of the pattern edge, and no undissolved material remaining during development or scum at the pattern edge The object is to provide a novel radiation-sensitive composition for forming a colored layer capable of forming a color filter with high color purity and a black matrix with high light shielding properties.
Other objects of the present invention include a color filter having a colored layer formed from the radiation-sensitive composition, a black matrix comprising the colored layer formed from the radiation-sensitive composition, and the color filter or black matrix. An object of the present invention is to provide a liquid crystal display element.
Still other objects and advantages of the present invention will become apparent from the following description.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator,
(D) The photopolymerization initiator is represented by the following formula (I)

(In formula (I), R ¹ , R ² and R ³ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. And the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is further represented by OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR. ²² -OCOR ²³ , -C (= N-OR ²¹ ) -R ²² , -C (= N-OCOR ²¹ ) -R ²² , CN, halogen atom, -CR ²¹ = CR ^{2 2} R ²³ , —CO—CR ²¹ ═CR ²² R ²³ , a carboxyl group, and an epoxy group may be substituted, and each of R ²¹ , R ^22, and R ²³ is independently a hydrogen atom or a carbon number of 1 to Represents an alkyl group having 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and the above R ¹¹ , R ¹² , R ¹³ , R ^21, a methylene group of the alkylene moiety of the substituents represented by R ²² and R ^23, unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, be interrupted 1 to 5 times by an amide bond or a urethane bond The alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. May even, also, R ¹² and R ¹³ and R ²² and R ²³ may be the respectively together form a ring, R ³ is form a ring together with the adjacent benzene ring R ⁴ and R ⁵ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group, and a and b are each independently 0 to 3.)
And is achieved by the radiation-sensitive composition used for forming the colored layer.

The above objects and advantages of the present invention are, secondly,
Achieved by a color filter having a colored layer formed from the radiation-sensitive composition or a black matrix comprising a colored layer formed from the radiation-sensitive composition;
This is achieved by a liquid crystal display device comprising the color filter or black matrix.
In the present invention, “radiation” includes visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc., and “colored layer” is a layer comprising a pixel array constituting a color filter or a black matrix itself. It means a certain layer.
In the present invention, the “color filter” includes at least a substrate and a pixel array (colored layer) of each color formed on the surface thereof, and further includes a black matrix, a transparent conductive film, a thin film transistor, a protective film, a spacer, and the like. You may have.

  The radiation-sensitive composition of the present invention can form a fine pattern without chipping and undercutting of the pattern edge even at a low exposure amount. In addition, undissolved material remains at the time of development or scum is formed on the pattern edge. Since it does not occur, it can be suitably applied to the formation of a colored layer composed of pixels constituting a color filter or a colored layer that is a black matrix.

Hereinafter, the present invention will be described in detail.
The radiation-sensitive composition of the present invention contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator.
(A) Colorant The colorant (A) contained in the radiation-sensitive composition of the present invention is not particularly limited in color tone, is appropriately selected according to the intended use of the colored layer, and is organically colored. An agent or an inorganic colorant may be used.
Examples of the organic colorant include organic pigments and natural pigments. Examples of the inorganic colorant include inorganic pigments and extender pigments.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically the following color index (C.I. I.) Numbers can be mentioned.
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180;
C. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51;
C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 215, C.I. I. Pigment red 242, C.I. I. Pigment red 254;
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 6;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

Examples of the inorganic pigment include lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black. etc;
Examples of the extender pigment include titanium oxide, barium sulfate, zinc white, and calcium carbonate.
Examples of the carbon black include furnace black, thermal black, acetylene black and the like, and specific examples thereof include furnace black, SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, MAF, FEF, FEF-HS, SRF, SRF-LM, SRF-LS, GPF, ECF, N-339, N-351, etc .;
Examples of the thermal black include FT and MT.
Examples of these commercially available products include, as SAF, Dia Black A (manufactured by Mitsubishi Chemical Corporation), Seast 9 (manufactured by Tokai Carbon Co., Ltd.) and the like;
Dia black SA (manufactured by Mitsubishi Chemical Corporation), SEAST 9H (manufactured by Tokai Carbon Co., Ltd.), etc. as SAF-HS;
Diablack I (manufactured by Mitsubishi Chemical Corporation), Seest 6 (manufactured by Tokai Carbon Co., Ltd.), etc. as ISAF;
As ISAF-LS, Dia Black LI (Mitsubishi Chemical Co., Ltd.), Seest 600 (Tokai Carbon Co., Ltd.), etc .;
As ISAF-HS Dia Black N234 (Mitsubishi Chemical Co., Ltd.), Seast 7HM (Tokai Carbon Co., Ltd.), etc .;
As HAF, Dia Black H (manufactured by Mitsubishi Chemical Corporation), Seest 3 (manufactured by Tokai Carbon Co., Ltd.), etc .;
HAAF-LS as Dia Black LH (Mitsubishi Chemical Co., Ltd.), Seest 300 (Tokai Carbon Co., Ltd.), etc .;
As HAF-HS, Dia Black SH (manufactured by Mitsubishi Chemical Corporation), Seast KH (manufactured by Tokai Carbon Co., Ltd.) and the like;
As MAF, Dia Black N550M (manufactured by Mitsubishi Chemical Corporation), Seast 116 (manufactured by Tokai Carbon Co., Ltd.), etc .;
As FEF, Diablack E (Mitsubishi Chemical Co., Ltd.), Seast SO, F, FM (Made by Tokai Carbon Co., Ltd.), etc. manufactured by Mitsubishi Chemical Corporation;
Diablack N760M (manufactured by Mitsubishi Chemical Corporation), HTC # SL (manufactured by Nippon Steel Chemical Co., Ltd.), etc. as SRF-LM;
Examples of GPF include Dia Black G (manufactured by Mitsubishi Chemical Corporation), Seast V (manufactured by Tokai Carbon Co., Ltd.), and the like.
These colorants may be used by modifying the particle surface with a polymer, if desired. The polymer coating method on the surface of carbon black is disclosed in, for example, Patent Document 2, Patent Document 3, and Patent Document 4.
The colorants can be used alone or in admixture of two or more.

When the radiation-sensitive composition of the present invention is used for forming a color filter, the color filter is required to have high-definition color development and heat resistance. Therefore, the colorant (A) has high color developability and heat resistance. A high colorant, particularly a colorant having high heat-resistant decomposability is preferable, specifically an organic colorant is preferable, and an organic pigment is particularly preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have a high light-shielding property, an organic pigment or carbon black is preferably used as the colorant (A). .
The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired.
As the dispersant, for example, various dispersants such as cationic, anionic, nonionic and amphoteric surfactants and polymer dispersants can be used, and among these, polymer dispersants are preferable. Specific examples include acrylic copolymers, modified acrylic copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branch polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include polymers composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.
Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161, Disperbyk as polyurethane. -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), as a cationic comb-type graft polymer, Solsperse 24000 (above, manufactured by Nippon Lubrizol Co., Ltd.) Etc., respectively.
These dispersants can be used alone or in admixture of two or more.
The amount of the dispersant used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the colorant (A).
Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

(B) Alkali-soluble resin (B) The alkali-soluble resin contained in the radiation-sensitive composition of the present invention can be used without any particular limitation to the remaining structure as long as it is alkali-soluble. The polymer (B-i) or polymer (B-ii) described is preferable.
The polymer (Bi) that can be preferably used as the (B) alkali-soluble resin in the present invention is represented by the following formula (B-1).

(In the formula (B-1), R ^I , R ^II and R ^III are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a monovalent organic having an acryloyl group or a methacryloyl group. Group, vinyl group or 1-methylvinyl group, Y is a divalent organic group, and h is an integer of 1 to 5.)
It is preferable that it is a polymer which has a structure represented by these.
In the above formula (B-1), R ^I and R ^II are preferably hydrogen atoms. R ^III is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. h is preferably 1.
As X in the above formula (B-1), the following formula (X-1) or (X-2)

(In Formula (X-1), R is a hydrogen atom or a methyl group, i is an integer of 2 to 5, j is an integer of 0 to 10,
In the formula (X-2), R is a hydrogen atom or a methyl group, Z is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a cyclohexane-1,2-diyl group, or a 1,2-phenylene group. It is. )
It is preferable that it is a monovalent group represented by these. In the above formula (X-1), i is preferably 2 or 5, and j is preferably an integer of 0 to 4. As Z in the formula (X-2), a 1,2-ethylene group is preferable.
Y in the above formula (B-1) is a methylene group, an alkylene group having 2 to 6 carbon atoms or an alkenylene group (however, these alkylene group and alkenylene group may be interrupted by an oxygen atom), cyclohexane. It is preferably a diyl group, a cyclohexenediyl group or an arylene group having 6 to 12 carbon atoms (however, this arylene group may have a carboxyl group or an acid anhydride group), and includes a methylene group, an ethylene group, 1 , 3-propylene group, 1,2-ethenylene group, 1,2-propenylene group, 1,3-propenylene group, 2,3-propenylene group, cyclohexane-1,2-diyl group, 4-cyclohexene-1 , 2-diyl group, a 1,2-phenylene group, a biphenyl -2-2'- diyl group or a group represented by the formula _-CH 2 -O-CH ₂ - Divalent group represented is more preferable.
In addition to the structure represented by the above formula (B-1), the polymer (Bi) preferably contained in the radiation-sensitive composition of the present invention is further represented by the following formula (B-2).

(In Formula (B-2), R ^IV is an aryl group having 6 to 10 carbon atoms or an alicyclic group having 3 to 10 carbon atoms.)
And a structure represented by the following formula (B-3)

(In formula (B-3), R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^X are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group.)
It is preferable that it has at least 1 type of structure selected from the group which consists of structure represented by these.
The aryl group having 6 to 10 carbon atoms ^{R IV} in the above formula (B-2), for example a phenyl group, o- hydroxyphenyl group, m- hydroxyphenyl group, p- hydroxyphenyl group, o- tolyl group, m -Toluyl group, p-toluyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, naphthyl group and the like;
Examples of the alicyclic group having 3 to 10 carbon atoms include a cyclohexyl group. R ^IV in the above formula (B-2) is preferably a phenyl group.
Examples of the halogen atom of R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^{X in} the above formula (B-3) include a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferable.
In the above formula (B-3), R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^X are all hydrogen atoms, or R ^VII is a chlorine atom, a hydroxyl group or a hydroxymethyl group And R ^V and R ^VI and R ^VIII , R ^IX and R ^X are all preferably hydrogen atoms, and R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^X are all hydrogen atoms. More preferably, R ^VII is a hydroxyl group and R ^V and R ^VI and R ^VIII , R ^IX and R ^X are all hydrogen atoms.
In the polymer (B-i) preferably contained in the radiation-sensitive composition of the present invention, the structure represented by the formula (B-1) is 5 to 5 times the total amount of the polymer (Bi). It is preferably 80% by weight, and more preferably 10 to 60% by weight. By making the ratio of the structure represented by the formula (B-1) in the polymer (Bi) within such a range, the developability of the radiation-sensitive composition containing the polymer becomes better, and at the time of development. Suppression of the generation of the residue becomes more effective, which is preferable.

The polymer (Bi) preferably contained in the radiation-sensitive composition of the present invention has a structure represented by the above formula (B-2) of 50% by weight based on the total amount of the polymer (Bi). % Or less, and more preferably 5 to 45% by weight. The polymer (Bi) preferably has the structure represented by the above formula (B-3) in a range of 60% by weight or less based on the total amount of the polymer (Bi). More preferably, it is in the range of ˜40% by weight. Furthermore, the polymer (Bi) may have both the structure represented by the above formula (B-2) and the structure represented by the above formula (B-3). The total content is preferably 80% by weight or less, more preferably 10 to 70% by weight, based on the total amount of the polymer (Bi). In this case, it is preferable that the individual content ratios of the structure represented by the above formula (B-2) or the structure represented by the above formula (B-3) are within the above-described ranges.
The colored layer formed by making the content rate of the structure represented by the said Formula (B-2) in the polymer (Bi) and the structure represented by the said Formula (B-3) into said range. The advantage that the adhesion to the substrate is further improved is preferable.
The polymer (Bi) preferably contained in the radiation-sensitive composition of the present invention has a polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC), preferably from 2,000 to 100, 000, more preferably 3,000 to 50,000. By making the weight average molecular weight of a polymer (Bi) into this range, the advantage that the solubility with respect to the solvent and developing solution of a polymer (Bi) improves more is acquired. For the polymer (Bi), the ratio Mw / Mn of polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by GPC is preferably 1.0 to 4.0, more preferably 1. 0-3.0. By making Mw / Mn of a polymer (Bi) into the said range, the advantage that the resolution | decomposability of the radiation sensitive composition obtained and the adhesiveness with respect to the board | substrate of the colored layer to be formed improves more.
Such a polymer (Bi) is, for example, the following formula (B-1 ′)

(In formula (B-1 ′), R ^I , R ^II , R ^III and h have the same meanings as in formula (B-1)).
A resin having a structure represented by the formula (hereinafter referred to as “styrene epoxy resin”), preferably a structure represented by the above formula (B-1 ′), a structure represented by the above formula (B-2), and A resin having at least one structure selected from the group consisting of the structure represented by (B-3) is represented by the following formula (a1):

(In formula (a1), X has the same meaning as in formula (B-1) above.)
(Hereinafter referred to as “unsaturated monocarboxylic acid (a1)”), and then the following formula (a2)

(In formula (a2), Y has the same meaning as in formula (B-1) above.)
(Hereinafter referred to as “polybasic acid anhydride (a2)”).
The styrene epoxy resin as described above is, for example, the following formula (b1)

(In the formula (b1), R ^I , R ^II , R ^III and h have the same meanings as in the above formula (B-1).)
It is preferable that it is a polymer of the compound (henceforth "compound (b1)") represented by these, or a copolymer of a compound (b1) and another radically polymerizable compound.
Specific examples of the compound (b1) include, for example, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl. Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethyl styrene, 2,4-diglycidyloxymethyl styrene, 2,5-diglycidyloxymethyl styrene, 2,6-di Glycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxy Methylstyrene, 2, 4 6- tri glycidyloxy-methylstyrene, and the like. Of these, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable. These compounds may be used in combination of two or more.
As said other radically polymerizable compound, following formula (b2)

(In formula (b2), R ^IV has the same meaning as in formula (B-2) above.)
(Hereinafter referred to as “compound (b2)”), a compound represented by the following formula (b3)

(In the formula (b3), R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^X have the same meanings as in the above formula (B-3).)
And a radically polymerizable compound other than the compounds (b1), (b2) and (b3) (hereinafter referred to as “compound (b4)”). be able to.
The compound (b2) leads the structure represented by the formula (B-2) to the polymer (Bi). Specific examples of the compound (b2) include, for example, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N- Examples thereof include m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N-cyclohexylmaleimide and the like. Of these, N-phenylmaleimide is preferred.
The compound (b3) leads the structure represented by the formula (B-3) to the polymer (Bi). Specific examples of the compound (b3) include acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene, 5-hydroxyacenaphthylene and the like. Of these, acenaphthylene and 5-hydroxyacenaphthylene are preferred.

Examples of the compound (b4) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxystyrene. , Indene, p-vinylbenzyl methyl ether and other aromatic vinyl compounds;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxytriethylene glycol Unsaturated carboxylic esters such as acrylate, methoxytriethylene glycol methacrylate, glycerin monomethacrylate;
Unsaturated amino acid esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Mention of a macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, etc. Can do.
These compounds (b4) can be used alone or in admixture of two or more.

When the styrene epoxy resin is a copolymer of the compound (b1) and another radical polymerizable compound, the copolymerization ratio of the compound (b1) and the other radical polymerizable compound is easy to synthesize the styrene epoxy resin. In consideration of the above, the structure represented by the above formula (B-1), the structure represented by the above formula (B-2) and the above formula (B-3) in the polymer (Bi) It can be appropriately set according to the desired value of the proportion of each structure.
For example, the copolymerization ratio of the compound (b1) is preferably 5 to 80% by weight, more preferably 10 to 60% by weight. If the copolymerization ratio of the compound (b1) exceeds 80% by weight, gelation tends to occur during the addition reaction of the unsaturated monocarboxylic acid (a1) described later, and the production may be difficult. On the other hand, when the copolymerization ratio of the compound (b1) is less than 5% by weight, the alkali solubility of the resin obtained as a result of the addition reaction of the styrene epoxy resin, the unsaturated monocarboxylic acid (a1) and the polybasic acid anhydride (a2) is low. If the radiation-sensitive composition containing this is used for the formation of the colored layer, there is a risk that a residue or background stain will occur on the unexposed portion of the substrate or on the light shielding layer.
The copolymerization ratio of the compound (b2) is preferably 50% by weight or less, more preferably 5 to 45% by weight. The copolymerization ratio of the compound (b3) is preferably 60% by weight or less, more preferably 5 to 40% by weight. In the copolymerization, the compounds (b2) and (b3) may be used together, and the copolymerization ratio in that case is preferably 80% by weight or less as the total amount of the compounds (b2) and (b3). More preferably, it is 5 to 70% by weight or less. When the compounds (b2) and (b3) are used in combination, the copolymerization ratio of each compound is preferably within the above-described range.

Styrene epoxy resins are especially
(1) Compound (b1),
(2) at least one of compounds (b2) and (b3), and (3) compound (b4)
In this case, the copolymerization ratio of each compound is 10 to 60% by weight per compound (b1), and at least one of compounds (b2) and (b3) (compound ( When b2) and (b3) are used in combination, the total amount is preferably 5 to 60% by weight and the compound (b4) is preferably 50% by weight or less.
The weight average molecular weight Mw of the styrene epoxy resin and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight can be appropriately set according to Mw and Mw / Mn of the desired polymer (Bi).
The styrene epoxy resin as described above can be produced, for example, by polymerizing the above compound or a mixture of compounds in a suitable solvent in the presence of a suitable radical polymerization initiator. As the solvent that can be used in the production of the styrene epoxy resin, for example, the same solvents described later can be used as the solvent used in the radiation-sensitive composition of the present invention. Examples of radical polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4). -Dimethylvaleronitrile) and the like.

The unsaturated monocarboxylic acid (a1) can be appropriately selected according to the desired type of X in the formula (B-1). Preferred examples of the unsaturated monocarboxylic acid (a1) include acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, and 2-methacryloyl. Roxyethyl succinic acid and the like can be mentioned. In the ω-carboxy-polycaprolactone monoacrylate and the ω-carboxy-polycaprolactone monomethacrylate, the number of repeating units of polycaprolactone is preferably 1 to 10, more preferably 2 to 4. Among the unsaturated monocarboxylic acids (a1), acrylic acid or methacrylic acid is particularly preferable because of its high reactivity. These can be used individually or in mixture of 2 or more types.
The addition reaction of the unsaturated monocarboxylic acid (a1) to the styrene epoxy resin can be performed according to a known method. For example, the addition reaction can be preferably performed in the presence of a solvent and an esterification catalyst at a temperature of 50 to 150 ° C. for 6 to 24 hours. Examples of the solvent that can be used here include propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3- Heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric n- butyl, can be given ethyl pyruvate.
Examples of esterification catalysts include tertiary amines such as triethylamine, trimethylamine, benzylmethylamine, benzyldiethylamine; quaternary compounds such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetrabutylammonium bromide. An ammonium salt or the like can be used. If necessary, polymerization inhibitors such as p-methoxyphenol and methylhydroquinone may be used. The amount of the esterification catalyst used is preferably 0.5 equivalent or less, more preferably 0.01 to 0.1 equivalent, based on the epoxy group of the styrene epoxy resin. The polymerization inhibitor is preferably used in an amount of 5,000 ppm or less, more preferably 500 to 3,000 ppm, based on the total amount of the reaction solution.

The amount of the unsaturated monocarboxylic acid (a1) used is preferably in the range of 0.7 to 1.3 equivalents, more preferably 0.9 to 1.1, with respect to 1 equivalent of the epoxy group of the styrene epoxy resin. The range is 2 equivalents.
The polybasic acid anhydride (a2) can be appropriately selected depending on the desired type of Y in the formula (B-1). Preferred polybasic acid anhydrides (a2) include, for example, malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, phthalic anhydride, Examples include cyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, diphenic anhydride, and the like. Of these, succinic anhydride, glutaric anhydride, phthalic anhydride or 4-cyclohexene-1,2-dicarboxylic anhydride is particularly preferable because of its high reactivity.
The addition reaction of the polybasic acid anhydride (a2) to the styrene epoxy resin can be performed under the same conditions as the addition reaction of the unsaturated monocarboxylic acid (a1) to the styrene epoxy resin. Following the addition reaction of the unsaturated monocarboxylic acid (a1) to the styrene epoxy resin, the polybasic acid anhydride (a2) may be added to the reaction mixture, and the addition reaction may be continued.
It is preferable that the usage-amount of a polybasic acid anhydride (a2) is the range of 0.2-1.0 equivalent with respect to 1 equivalent of epoxy groups of a styrene epoxy resin, More preferably, it is 0.4-0. The range is 9 equivalents.

（式（Ｂ−４）において、Ｒ^ＸＩは水素原子またはメチル基である。）
で表される構造と、
上記式（Ｂ−２）で表される構造および上記式（Ｂ−３）で表される構造よりなる群から選択される少なくとも１種の構造とを有する重合体である。
重合体（Ｂ−ｉｉ）は、上記式（Ｂ−４）で表される構造を、重合体（Ｂ−ｉｉ）の全量に対して１〜５０重量％の範囲で有することが好ましく、５〜４０重量％の範囲で有することがより好ましい。重合体（Ｂ−ｉｉ）は、上記式（Ｂ−２）で表される構造を、重合体（Ｂ−ｉｉ）の全量に対して１〜５０重量％の範囲で有することが好ましく、５〜４５重量％の範囲で有することがより好ましい。重合体（Ｂ−ｉｉ）は、上記式（Ｂ−３）で表される構造を、重合体（Ｂ−ｉｉ）の全量に対して１〜６０重量％の範囲で有することが好ましく、５〜４５重量％の範囲で有することがより好ましい。重合体（Ｂ−ｉｉ）は、上記式（Ｂ−２）で表される構造および上記式（Ｂ−３）で表される構造の双方を有していてもよく、この場合の重合体（Ｂ−ｉｉ）におけるこれらの構造の含有割合は、それぞれ上記の範囲内であって、且つ両者の合計が５〜８０重量％であることが好ましく、１０〜７０重量％であることがより好ましい。
本発明の感放射線性組成物に好ましく含有される重合体（Ｂ−ｉｉ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量Ｍｗが、好ましくは２，０００〜５００，０００であり、より好ましくは５，０００〜１００，０００である。
かかる重合体（Ｂ−ｉｉ）は、例えば下記式（ｂ５）

（式（ｂ５）において、Ｒ^ＸＩは上記式（Ｂ−４）におけるのと同じ意味である。）
で表される化合物（以下、「化合物（ｂ５）」という。）と、化合物（ｂ２）および化合物（ｂ３）よりなる群から選択される少なくとも１種の化合物と、任意的に化合物（ｂ４）との共重合体であることが好ましい。
上記化合物（ｂ５）としては、（メタ）アクリル酸を好ましく使用することができる。
化合物（ｂ５）、（ｂ２）、（ｂ３）および（ｂ４）の使用割合は所望の重合体（Ｂ−ｉｉ）の構造に応じて適宜に設定することができ、これらの共重合反応は、上記のスチレンエポキシ樹脂の合成に準じて行うことができる。
本発明の感放射線性組成物は、上記の如き（Ｂ）アルカリ可溶性樹脂を、（Ａ）着色剤１００重量部に対して好ましくは１０〜２００重量部、より好ましくは２０〜１５０重量部含有する。この値が１０重量部未満であると、感度不足により形成される着色層の硬度が不足する場合があり、一方２００重量部を超えると得られるカラーフィルターの色純度またはブラックマトリックスの遮光性が不足する場合がある。 The polymer (B-ii) that can be preferably used as the (B) alkali-soluble resin in the present invention is represented by the following formula (B-4).

(In the formula (B-4), R ^XI is a hydrogen atom or a methyl group.)
And a structure represented by
It is a polymer having at least one structure selected from the group consisting of the structure represented by the above formula (B-2) and the structure represented by the above formula (B-3).
The polymer (B-ii) preferably has the structure represented by the formula (B-4) in the range of 1 to 50% by weight with respect to the total amount of the polymer (B-ii). More preferably, it is in the range of 40% by weight. The polymer (B-ii) preferably has the structure represented by the above formula (B-2) in the range of 1 to 50% by weight with respect to the total amount of the polymer (B-ii). It is more preferable to have it in the range of 45% by weight. The polymer (B-ii) preferably has a structure represented by the above formula (B-3) in a range of 1 to 60% by weight based on the total amount of the polymer (B-ii). It is more preferable to have it in the range of 45% by weight. The polymer (B-ii) may have both a structure represented by the above formula (B-2) and a structure represented by the above formula (B-3). In this case, the polymer ( The content ratios of these structures in B-ii) are each in the above range, and the total of both is preferably 5 to 80% by weight, and more preferably 10 to 70% by weight.
The polymer (B-ii) preferably contained in the radiation-sensitive composition of the present invention has a polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC), preferably 2,000 to 500, 000, more preferably 5,000 to 100,000.
Such a polymer (B-ii) is, for example, the following formula (b5)

(In the formula (b5), R ^XI has the same meaning as in the above formula (B-4).)
A compound represented by formula (hereinafter referred to as “compound (b5)”), at least one compound selected from the group consisting of compound (b2) and compound (b3), and optionally compound (b4) It is preferable that it is a copolymer.
As the compound (b5), (meth) acrylic acid can be preferably used.
The use ratio of the compounds (b5), (b2), (b3) and (b4) can be appropriately set according to the structure of the desired polymer (B-ii). This can be carried out according to the synthesis of styrene epoxy resin.
The radiation-sensitive composition of the present invention contains (B) the alkali-soluble resin as described above, preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, based on 100 parts by weight of the (A) colorant. . If this value is less than 10 parts by weight, the hardness of the colored layer formed due to insufficient sensitivity may be insufficient. On the other hand, if it exceeds 200 parts by weight, the color purity of the obtained color filter or the light blocking property of the black matrix is insufficient. There is a case.

(C) Multifunctional monomer Examples of the (C) polyfunctional monomer in the radiation-sensitive composition of the present invention include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Polyacrylates or polymethacrylates of polyhydric alcohols having a valence of 3 or more, such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol;
A polyacrylate or polymethacrylate of a dicarboxylic acid-modified product of the above-mentioned trihydric or higher polyhydric alcohol;
Oligoacrylate or oligomethacrylate such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Diacrylates or dimethacrylates of hydroxylated polymers at both ends such as both ends hydroxypolybutadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone;
Examples thereof include trisacryloyloxyethyl phosphate and trismethacryloyloxyethyl phosphate. Among the above, “polyacrylate or polymethacrylate of a dicarboxylic acid modified product of a trihydric or higher polyhydric alcohol” means a polyester of a monoester compound in which one dicarboxylic acid is added to a trivalent or higher polyvalent carboxylic acid. Or polymethacrylate.
Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and polyacrylates or polymethacrylates of dicarboxylic acid modified products of trihydric or higher polyhydric alcohols are preferable. Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate Examples include methacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. Of the above, succinic acid-modified pentaerythritol triacrylate and succinic acid-modified pentaerythritol trimethacrylate

(In the above formula, R ^XI is a hydrogen atom or a methyl group, respectively.)
Among these polyfunctional monomers, which are compounds represented by the formula, in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate has a high strength of the resulting colored layer, and the surface of the colored layer This is preferable in that it is excellent in smoothness and hardly causes scumming or film residue in a region other than the portion where the pattern of the colored layer is formed.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.
The use ratio of the (C) polyfunctional monomer in the radiation-sensitive composition of the present invention is preferably 5 to 500 parts by weight, more preferably 20 parts per 100 parts by weight of the (B) alkali-soluble resin. -300 parts by weight. (C) If the use ratio of the polyfunctional monomer is less than 5 parts by weight, the strength of the colored layer and the smoothness of the colored layer surface may be insufficient. In some cases, developability is insufficient, or background contamination or film residue is likely to occur in a region other than the portion where the pattern of the colored layer is formed.
In the radiation-sensitive composition of the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer.
Specific examples of such monofunctional monomers include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate. , Methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, etc. Furthermore, as a commercial product, M-5300 (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.
The amount of the monofunctional monomer used is preferably 90% by weight or less, more preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. .

(D) Photopolymerization initiator The photopolymerization initiator contained in the radiation-sensitive composition of the present invention is the above-mentioned (C) by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a component that generates radicals capable of initiating polymerization of a polyfunctional monomer and optionally a monofunctional monomer. The photopolymerization initiator in the present invention is a compound represented by the above formula (I).
The compound represented by the above formula (I) has geometric isomers due to the double bond of oxime, but these are not distinguished from each other. The above general formula (I) and the exemplified compounds described below are a mixture of both. Or it represents either one, and it is not limited to the structure which showed the isomer.
In the above formula ^(I), the alkyl group represented by ^{R 11, R 12, R 13} , R 21, R 22 and ^{R 23,} for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, t-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl Group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, otatadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, vinyl group, allyl group, butenyl group, ethynyl group, propynyl group , Methoxyethyl group, ethoxyethyl group, propoxyethyl group, pentyloxyethyl Group, octyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, methoxypropyl group, 2-methoxy-1-methylethyl group and the like. The aryl group represented by ^{R 11, R 12, R 13} , R 21, R 22 and ^{R 23,} for example, a phenyl group, a tolyl group, xylyl group, ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthryl group, Examples thereof include a phenanthrenyl group, a substituted phenyl group substituted with one or more alkyl groups, a substituted biphenylyl group, a substituted naphthyl group, and a substituted anthryl group. Examples of the arylalkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, A phenylethyl group, a phenylethenyl group, etc. are mentioned. Examples of the heterocyclic group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include a pyridyl group, a pyrimidyl group, a furyl group, a chenyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazole. 2- to 7-membered groups such as 2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolicyl group, pyrazolysyl group, thiasolysyl group, inchazolysyl group, oxasolysyl group, isoxasolysyl group, piperidyl group, piperazyl group, morpholinyl group, etc. Heterocyclic groups are preferred. In addition, as a ring that R ¹² and R ¹³ can form together, a ring that R ²² and R ²³ can form together, and a ring that R ³ can form together with an adjacent benzene ring Examples thereof include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentine ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. Examples of the halogen atom that may substitute R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ^22, and R ²³ and the halogen atom represented by R ⁴ , R ⁵ include fluorine, chlorine, bromine, and iodine. Can be mentioned.

The alkylene part of the above substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. Alternatively, two or more kinds of groups may be used, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. The alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.
Among the compounds represented by the formula (I), in the general formula (I), R ¹ is an alkyl group having ¹¹ to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. Arylalkyl group, a heterocyclic group having 2 to 20 carbon atoms, OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, or R ³ is an ether bond or an ester bond 1 to 5 times Interrupted alkyl group having 1 to 12 carbon atoms, alkyl group having 13 to 20 carbon atoms, OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, in particular, R ¹ is carbon An alkyl group having 11 to 20 atoms or an aryl group having 6 to 30 carbon atoms, or a methylene group in the alkylene part of R ³ is a ter bond or an ether. A branched alkyl group having 8 or more carbon atoms which may be interrupted 1 to 5 times by a steal bond; the methylene group of the alkylene part of the alkyl group is interrupted 1 to 5 times by a steric bond or an ester bond An alkyl group having 13 or more carbon atoms; R ³ is an alkyl group interrupted 1 to 5 times by an ether bond; R ³ is interrupted 1 to 5 times by an ester bond An alkyl group is preferred because it is easy to synthesize and has high sensitivity, and when it is used as the (D) radiation-sensitive polymerization initiator in the radiation-sensitive resin composition of the present invention, it has a high solubility in a solvent.
The compound represented by the above formula (I) may be dimerized via R ¹ or R ² as shown in the following formula.

(In the above formula, R ^{1 to} R ⁵ and a and b have the same meanings as in the above formula (I).)
Accordingly, preferred specific examples of the compound represented by the above formula (I) include the following compound Nos. 1-No. 71.

Although the manufacturing method of the compound represented by the said formula (I) is not specifically limited, For example, according to the following reaction formula, it can manufacture with the following method.
First, the nitrocarbazole compound 1 having the desired R ⁴ and R ⁵ and the acid chloride 2 having the desired R ¹ are reacted in ethylene dichloride (EDC) in the presence of zinc chloride to obtain the acyl compound 3. . Next, the oxime compound 4 is obtained by reacting the acyl compound 3 with hydroxylamine hydrochloride in the presence of N, N-dimethylformamide (DMF). Next, the compound represented by the above formula (I) can be obtained by reacting the oxime compound 4 with the acid anhydride 5 or acid chloride 5 ′ having the desired R ² .

The compounds represented by the above formula (I) can be used alone or in admixture of two or more.
In the present invention, the amount of the (D) photopolymerization initiator used is preferably 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer optionally used. 0.01 to 500 parts by weight, more preferably 1 to 300 parts by weight, and particularly preferably 10 to 200 parts by weight. (D) If the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate and it may become difficult to obtain the pattern array by which the pattern of the colored layer was arrange | positioned according to the predetermined arrangement | sequence. On the other hand, if it exceeds 500 parts by weight, the formed colored layer tends to fall off from the substrate during development, and it may be easy to cause soiling or film residue on the unexposed portion of the substrate or the light shielding layer. .
In the radiation-sensitive composition of the present invention, a part of the (D) photopolymerization initiator as described above may be replaced with another photopolymerization initiator. Examples of other photopolymerization initiators that can be used here include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthones. Compound, diazo compound and the like.

Specific examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1. -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime) and the like;
Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl- , 2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis ( 2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like;
Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy Triazine compounds having a halomethyl group such as (tyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned respectively.

When the biimidazole compound is used as another photopolymerization initiator, it is preferable to further use a hydrogen donor in terms of further improving the sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound.
Specific examples of the mercaptan compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5. -Dimethylaminopyridine and the like;
Specific examples of the amine compound include, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and ethyl-4. -Dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, etc. can be mentioned, respectively.

  In the radiation-sensitive composition of the present invention, when a part of (D) the photopolymerization initiator is replaced with another photopolymerization initiator, the amount of the other photopolymerization initiator used is (D) light It is preferable that it is 50 weight% or less with respect to the whole quantity of a polymerization initiator.

Other Additives The radiation-sensitive composition of the present invention contains the above-mentioned (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photopolymerization initiator. In addition, various other additives can be contained as required.
Examples of such other additives include a filler, a surfactant, an adhesion promoter, an antioxidant, an antioxidant, an anti-aggregation agent, and a development modifier.
Examples of the filler include glass, alumina and the like;
Examples of the surfactant include a nonionic surfactant, a cationic surfactant, and an anionic surfactant;
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like;
Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the like;
Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and the like;
Examples of the aggregation inhibitor include sodium polyacrylate and the like.

The developability modifier is added to improve the solubility of the coating film formed from the radiation-sensitive composition of the present invention in an alkaline developer and to further suppress the remaining undissolved material after development. Can do. Examples of such developability modifiers include organic acids. As such an organic acid, an aliphatic carboxylic acid having a molecular weight of 1,000 or less or a carboxylic acid having a benzene ring is preferable.
Specific examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.
Examples of the carboxylic acid having a benzene ring include an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain, and specific examples thereof. For example, aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
In addition to trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.
Of these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble and soluble in solvents described below. From the viewpoint of prevention of background contamination and film residue in a region other than the portion where the colored layer is formed.
The organic acids can be used alone or in admixture of two or more.
The use amount of the developability modifier in the present invention is preferably 10% by weight or less, more preferably 0.001 to 10% by weight, still more preferably 0.001% by weight, based on the whole radiation-sensitive composition. 01 to 1% by weight. When the usage-amount of a developability modifier exceeds 10 weight%, the adhesiveness with respect to the board | substrate of the formed colored layer may be insufficient.

Solvent The radiation-sensitive composition of the present invention comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator as essential components. Although it contains other additives, it is preferably prepared as a liquid composition in which each component other than (A) the colorant is dissolved in an appropriate solvent and (A) the colorant is uniformly dispersed.
As the solvent, (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator and other additives are dispersed or dissolved and reacted with these components. As long as it has moderate volatility, it can be appropriately selected and used.
Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri Propylene glycol monomethyl ether , And tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ethoxy ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-acetate -Propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyrate Butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, DOO methyl acetate, ethyl acetoacetate, other esters such as ethyl 2-oxo acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.
These solvents can be used alone or in admixture of two or more.

Further, together with the solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , Γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and other high boiling point solvents may be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
Among the solvents, from the viewpoints of solubility, pigment dispersibility, coatability, etc., ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, cyclohexanone, 2 -Heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, acetic acid n- Butyl, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. are preferred and high boiling The solvent γ- butyrolactone are preferable.
The amount of the solvent used in the radiation-sensitive composition of the present invention is preferably 100 to 10,000 parts by weight, more preferably 100 parts by weight of (B) alkali-soluble resin as the total amount of the solvent including the high boiling point solvent. 500 to 5,000 parts by weight. When the solvent in the radiation sensitive composition of the present invention contains a high boiling point solvent, the amount of the high boiling point solvent used is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the solvent. It is.

The method of forming the colored layer Next, using the radiation-sensitive composition of the present invention, a method for forming a colored layer. First, the case where the colored layer is a layer made of a pixel array constituting a color filter will be described, and then the case where the colored layer is a black matrix will be described.
[Method for forming colored layer comprising pixel array]
First, a light shielding layer (black matrix) is formed so as to define a pixel forming portion on the surface of the substrate, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed is formed on the substrate. After coating, a heat treatment (pre-baking) is performed to evaporate and remove the solvent to form a coating film. Next, after exposing a partial area of the coating film with radiation, it is developed using an alkali developer to dissolve and remove the non-exposed portion of the coating film, and further subjected to a heat treatment (post-bake) to obtain a red color. A pixel array in which pixels are arranged in a predetermined pattern is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, application of each liquid composition, pre-baking, exposure and development are performed in the same manner as described above to obtain a green pixel array. By sequentially forming the blue and blue pixel arrays on the same substrate, a color filter in which the pixel arrays (colored layers) of the three primary colors of red, green and blue are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixel arrays of the respective colors is not particularly limited.
Examples of the substrate used when forming the colored layer include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

The method for applying the radiation-sensitive composition to the substrate is not particularly limited. For example, a method using a slit nozzle such as a slit and spin coating method or a slit die coating method (hereinafter referred to as “slit nozzle coating”). Law ”)).
The coating conditions in the slit nozzle coating method vary depending on the slit-and-spin coating method, the spinless coating method, the size of the coated substrate, etc., but for example, a fifth-generation glass substrate (1,100 mm × 1, 250 mm), the discharge amount of the radiation-sensitive composition from the slit nozzle is, for example, 500 to 2,000 microliters / second, preferably 800 to 1,500 microliters / second, and the coating speed. Is preferably 500 to 1,500 mm / second, more preferably 700 to 1,200 mm / second.
The solid content concentration of the radiation-sensitive composition used in the slit nozzle coating method (the ratio of the total weight of components other than the solvent in the composition to the total weight of the composition) is preferably 10 to 20% by weight, more preferably Is 13 to 18% by weight.
When the slit nozzle coating method is employed, pre-baking is preferably “vacuum baking” performed under reduced pressure, and the vacuum baking conditions are preferably a vacuum degree of 10 to 150 Pa, more preferably about 25 to 75 Pa. The temperature is preferably 60 to 120 ° C, more preferably about 70 to 110 ° C, and the baking time is preferably 1 to 5 minutes, more preferably about 2 to 4 minutes.
The thickness of the coating film to be formed is, for example, 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm, as the film thickness after removal of the solvent.
Thereafter, at least a part of the formed coating film is exposed. The partial area of the coating film can be exposed by, for example, irradiating with radiation through a photomask having an appropriate pattern.
As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Of these, radiation having a wavelength in the range of 190 to 450 nm is preferable.
The exposure dose of radiation is, for example, about 10 to 10,000 J / m ² .

Then, it develops using a developing solution and melt | dissolves and removes the unexposed part of a coating film.
Examples of the developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- An alkaline developer composed of an aqueous solution such as [4.3.0] -5-nonene is preferable.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After alkali development, it is preferably washed with water.
As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be employed.
The development conditions are preferably about 5 to 300 seconds at room temperature.
Thereafter, the colored layer can be formed on the substrate by post-baking.
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
The above steps are repeated in any order using each colored layer forming composition in which a red, green, or blue pigment is dispersed, thereby obtaining a red pixel array, a green pixel array, and a blue pixel array. A color filter having a (colored layer) formed on the same substrate can be obtained.

[Method for forming colored layer as black matrix]
In the “method for forming a colored layer comprising a pixel array”, the above steps are sequentially performed using a radiation-sensitive composition in which a black pigment or a mixture of a red pigment, a yellow pigment and a blue pigment is dispersed as a composition. Thus, it is possible to obtain a substrate in which the black matrix pattern is arranged in a predetermined arrangement.
A color filter having a colored layer formed as described above or a black matrix comprising a colored layer is extremely useful for, for example, a color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

Liquid crystal display device The liquid crystal display device of the present invention comprises a color filter having a colored layer formed from the radiation-sensitive composition of the present invention or a black matrix comprising a colored layer formed of the radiation-sensitive composition of the present invention. To do.
The liquid crystal display element of the present invention can have an appropriate structure. For example, a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. A substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an electrode made of ITO (indium oxide doped with tin) is formed. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition color liquid crystal display element can be obtained.
Other specific embodiments of the liquid crystal display element will be apparent to those skilled in the art.
The liquid crystal display element of the present invention is excellent in color purity.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
<Preparation of pigment dispersion>
Preparation Example 1
(A) C.I. I. Pigment red 254 and C.I. I. 15.0 parts by weight of a mixture consisting of CI Pigment Red 177 (mixing ratio = 80: 20 (weight ratio)), 4.0 parts by weight of Disperbyk-2000 as a dispersant in terms of solid content, and propylene glycol monomethyl ether acetate as a solvent, A pigment dispersion (A-1) was prepared by treating these with a bead mill using a solid content of 19% by weight.
Preparation Example 2
(A) C.I. I. Pigment green 36 and C.I. I. 15.0 parts by weight of a mixture consisting of CI Pigment Yellow 150 (mixing ratio = 60: 40 (weight ratio)), 4.0 parts by weight of Disperbyk-2001 as a dispersant, and 3-methoxybutyl acetate as a solvent, A pigment dispersion (A-2) was prepared by using a solid content concentration of 19% by weight and treating them with a bead mill.
Preparation Example 3
(A) 20.0 parts by weight of carbon black as a colorant, 4.0 parts by weight of Disperbyk-167 as a dispersant in terms of solids, 3-methoxybutyl acetate as a solvent, and a solids concentration of 24% by weight And a pigment dispersion (A-3) was prepared by treating them with a bead mill.

<(B) Synthesis of alkali-soluble resin>
Synthesis example 1
In a flask equipped with a condenser and a stirrer, 20.0 g of methacrylic acid, 35.0 g of N-phenylmaleimide, 11.0 g of styrene, 24.0 g of benzyl methacrylate and 10.0 g of 2-hydroxyethyl methacrylate were mixed with propylene glycol monomethyl ether acetate. Dissolved in 200 g, 3.0 g of 2,2′-azobisisobutyronitrile and 5.0 g of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring, and polymerized for 5 hours while maintaining this temperature to obtain a solution containing 33% by weight of the alkali-soluble resin [BI]. This alkali-soluble resin [BI] had a polystyrene equivalent weight average molecular weight (Mw) of 12,000.
Synthesis example 2
In a flask equipped with a condenser and a stirrer, 34.0 g of p-vinylbenzylglycidyl ether, 43.0 g of N-phenylmaleimide, 7.0 g of styrene, and 16.0 g of benzyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate. Further, 8.0 g of 2,2′-azobisisobutyronitrile and 8.0 g of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and polymerized for 5 hours.
Next, 17 g of methacrylic acid (1.1 equivalent to p-vinylbenzylglycidyl ether), 0.9 g of p-methoxyphenol and 1.7 g of tetrabutylammonium bromide were added to the reaction solution, and 9 g at a temperature of 120 ° C. Time reaction was performed. Further, 14.3 g of succinic anhydride (0.9 equivalent to p-vinylbenzylglycidyl ether) and 1.7 g of tetrabutylammonium bromide were added and reacted at a temperature of 100 ° C. for 6 hours. The solution was washed twice with the temperature maintained at 85 ° C. and concentrated under reduced pressure to obtain a solution containing 33% by weight of the alkali-soluble resin [B-II]. This alkali-soluble resin [B-II] had a weight average molecular weight (Mw) in terms of polystyrene of 8,500.

<Preparation and evaluation of radiation-sensitive composition>
Example 1
Preparation of Radiation Sensitive Composition (A) 100 parts by weight of the pigment dispersion (A-1) obtained in Preparation Example 1 as a colorant, and (B) an alkali-soluble resin [BI] as an alkali-soluble resin solution An amount corresponding to 13 parts by weight in terms of the resin [BI] in the solution, (C) 13 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) the above compound as a photopolymerization initiator No. 33 parts by weight and 1 part by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name “Irgacure 369” manufactured by Ciba Specialty Chemicals) As a solvent, ethyl 3-ethoxypropionate was mixed to prepare a radiation sensitive composition (S-1) having a solid concentration of 20% by weight.
About the obtained radiation sensitive composition (S-1), it evaluated according to the following procedure. The evaluation results are shown in Table 2.
Residue evaluation After applying the radiation-sensitive composition (S-1) obtained above onto a glass substrate surface-treated for 1 minute in a hexamethyldisilazane (HMDS) atmosphere heated to 60 ° C. using a spin coater And prebaking on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 1.7 μm.
Next, the substrate was cooled to room temperature, shower-developed with a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with ultrapure water, and then air-dried. This substrate was observed with an optical microscope, and it was evaluated whether or not residues remained on the substrate.

Evaluation of Adhesion and Sensitivity After applying the radiation sensitive composition (S-1) to a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface using a spin coater, 90 ° C. Was baked on the hot plate for 2 minutes to form a coating film having a thickness of 1.7 μm.
Next, the substrate is cooled to room temperature, and then passed through a photomask having a plurality of slits having different sizes in a width range of 5 to 50 μm, and a high-pressure mercury lamp (Type 1) having the spectrum distribution of Type 1 shown in FIG. 1 light source), and the coating film was exposed at an exposure amount of 1,000 J / m ² . Thereafter, the substrate was subjected to shower development using a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, then washed with ultrapure water and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which red stripe pixel patterns were arranged on the substrate. At this time, the substrate can be observed with an optical microscope to check whether or not the edge of the pixel pattern is chipped, and the minimum width of the remaining pixel pattern can be formed without peeling off the entire pattern. The minimum pattern size (μm) was evaluated. It can be said that the smaller the minimum pattern size that can be formed is, the better the adhesion is.
Further, the line width of the pattern formed through a photomask having a width of 30 μm was measured by observation with an optical microscope. It can be said that the greater the pattern line width, the higher the sensitivity.
Evaluation of sensitivity when exposure wavelength is changed In the above " Evaluation of adhesion and sensitivity", instead of the light source of Type 1, high-pressure mercury having respective spectral distributions of Type 2, Type 3, and Type 4 shown in FIGS. Except that each lamp (type 2 to type 4 light source) was used, a pixel array in which red stripe pixel patterns were arranged on a substrate was formed in the same manner as in “Evaluation of Adhesion and Sensitivity”. The line width of the pattern formed through a photomask having a width of 30 μm was measured by observation with an optical microscope. As the light source changes from Type 1 to Type 2, Type 3, and Type 4, light in the short wavelength region is gradually cut. Even when these light sources are used, it can be said that the higher the pattern line width, the higher the sensitivity.

Examples 2-12 and Comparative Examples 1-3
In Example 1, the radiation-sensitive compositions (S-2) to (S-12) and the same as in Example 1 except that the types and amounts used of the respective components were changed as shown in Table 1. (S-1) to (s-3) were prepared and evaluated. The evaluation results are shown in Table 2.
Abbreviations of each component in Table 1 have the following meanings.
(C) Polyfunctional monomer C-1: Dipentaerythritol hexaacrylate (trade name “M-402”, manufactured by Toagosei Co., Ltd.)
(D) Photopolymerization initiator D-1: Compound No. 33
D-2: Compound No. 37
D-3: Compound No. 50
D-4: Compound No. 54
D-5: Compound No. 69
D-6: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name “Irgacure 369”, manufactured by Ciba Specialty Chemicals)
D-7: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name “IRGACURE OX02”, Ciba Specialty Chemicals)
Solvent EEP: Ethyl 3-ethoxypropionate PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate In Examples 1 and 2 and Comparative Examples 1 and 2, two types of photopolymerization initiators were used. .

The spectrum distribution map of the light source of Type 1. The spectrum distribution map of the light source of Type 2. The spectrum distribution map of the light source of Type 3. The spectrum distribution map of the light source of Type 4.

Claims (9)

A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator,
(D) The photopolymerization initiator is represented by the following general formula (I)

(Wherein R ¹ , R ² and R ³ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each represented by Independently, it represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, alkyl group, a hydrogen atom of the aryl group, arylalkyl group and heterocyclic group may further ^{oR 21, COR 21, SR 21} , NR 22 R 23, CONR 22 R 23, -NR 22 -OR 23, -NCOR 22 -OCOR ^{23, -C (= N-OR} 21) -R 22, -C (= N-OCOR 21) -R 22, CN, halogen ^atom, -CR 21 ^{= CR} 22 ^{R 2 , -CO-CR 21 = CR 22} R 23, carboxyl group, may be substituted with an epoxy ^group, R ^{21, R 22} and ^{R 23} each independently represent a hydrogen atom, an alkyl having 1 to 20 carbon atoms Group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and the above R ¹¹ , R ¹² , R ¹³ , R ²¹ , R The methylene group of the alkylene part of the substituent represented by ²² and R ²³ may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, or the alkyl terminal of the substituent may be an unsaturated bond. R ¹² and R ¹³ and R ²² and R ²³ may be combined to form a ring, and R ³ may be combined with an adjacent benzene ring to form a ring. R ⁴ and R ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ CSOR ¹¹ , CN, a halogen atom or a hydroxyl group, and a and b are each independently 0 to 3.)
A radiation-sensitive composition, characterized by being used in the formation of a colored layer. (B) The alkali-soluble resin is represented by the following formula (B-1)

(In the formula (B-1), R ^I , R ^II and R ^III are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a monovalent organic having an acryloyl group or a methacryloyl group. Group, vinyl group or 1-methylvinyl group, Y is a divalent organic group, and h is an integer of 1 to 5.)
The radiation sensitive composition of Claim 1 which is a polymer which has a structure represented by these. X in the above formula (B-1) is the following formula (X-1) or (X-2)

(In Formula (X-1), R is a hydrogen atom or a methyl group, i is an integer of 2 to 5, j is an integer of 0 to 10,
In the formula (X-2), R is a hydrogen atom or a methyl group, Z is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a cyclohexane-1,2-diyl group, or a 1,2-phenylene group. It is. )
A monovalent group represented by
Y is a methylene group, an alkylene group having 2 to 6 carbon atoms or an alkenylene group (however, these alkylene groups and alkenylene groups may be interrupted by an oxygen atom in the middle), cyclohexanediyl group, cyclohexenediyl group or carbon number 6 The radiation-sensitive composition according to claim 2, which is -12 arylene groups (wherein the arylene group may have a carboxyl group or an acid anhydride group). (B) In addition to the structure represented by the above formula (B-1), the alkali-soluble resin is further represented by the following formula (B-2)

(In Formula (B-2), R ^IV is an aryl group having 6 to 10 carbon atoms or an alicyclic group having 3 to 10 carbon atoms.)
And a structure represented by the following formula (B-3)

(In formula (B-3), R ^V , R ^VI , R ^VII , R ^VIII , R ^IX and R ^X are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group.)
The radiation sensitive composition of Claim 2 or 3 which is a polymer which has at least 1 type of structure selected from the group which consists of a structure represented by these. (B) The alkali-soluble resin is represented by the following formula (B-4).

(In the formula (B-4), R ^XI is a hydrogen atom or a methyl group.)
And a structure represented by
The polymer having at least one structure selected from the group consisting of the structure represented by the formula (B-2) and the structure represented by the formula (B-3). Radiation sensitive composition.   The color filter which has a colored layer formed from the radiation sensitive composition as described in any one of Claims 1-5.   A liquid crystal display device comprising the color filter according to claim 6.   The black matrix which consists of a colored layer formed from the radiation sensitive composition as described in any one of Claims 1-5.   A liquid crystal display device comprising the black matrix according to claim 8.

Images