JP6464764B2 - Radiation-sensitive coloring composition, spacer, method for forming the same, and liquid crystal display device - Google Patents

Description

  The present invention relates to a radiation-sensitive colored composition, a colored pattern, a method for forming the same, and a liquid crystal display element.

  There is a method of using photolithography to form a spacer for maintaining a distance (cell gap) between substrates in a liquid crystal display element. In this method, a radiation-sensitive composition is applied onto a substrate, exposed to radiation such as ultraviolet rays through a predetermined mask, and then developed to form a dot or stripe pattern as a spacer (special feature). No. 2001-302712).

  In recent years, a so-called black column spacer in which a spacer is provided with a light-shielding property by a colorant such as carbon black has also been proposed (see JP 2011-170075 A). However, when a coloring pattern such as a black column spacer is employed, the liquid crystal layer is easily contaminated due to elution of the colorant in the coloring pattern into the liquid crystal layer. Such contamination of the liquid crystal layer causes a decrease in the voltage holding ratio of the liquid crystal display element.

JP 2001-302712 A JP 2011-170075 A

  The present invention has been made based on the circumstances as described above, and an object of the present invention is to provide a radiation-sensitive colored composition capable of forming a colored pattern in which contamination of a liquid crystal layer by a colorant is reduced, and the radiation sensitivity. It is providing the coloring pattern formed from a coloring composition, its formation method, and a liquid crystal display element provided with this coloring pattern.

（式（１）中、Ｒ^Ｘは１価の有機基を表す。） The invention made in order to solve the above problems is a polymer (hereinafter also referred to as “[A] polymer”), photopolymerization having two or more sites represented by the following formula (1) in one molecule. Initiator (hereinafter also referred to as “[B] photopolymerization initiator”) and a colorant having a lactam structure, this isomer ring structure or a combination thereof (hereinafter also referred to as “[C] colorant”). Is a radiation-sensitive colored composition.

(In the formula (1), R ^X represents a monovalent organic group.)

The colorant preferably has at least one of a site represented by the following formula (2) and a site represented by the following formula (3).

（式（４）及び式（５）中、Ｒ^１、Ｒ^６、Ｒ^１１及びＲ^１６は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜６のアルキル基又は炭素数１〜６のフッ化アルキル基である。
Ｒ^２〜Ｒ^５、Ｒ^７〜Ｒ^１０、Ｒ^１２〜Ｒ^１５及びＲ^１７〜Ｒ^２０は、それぞれ独立して、水素原子、ハロゲン原子、又はＲ^２１、ＣＯＯＨ、ＣＯＯＲ^２１、ＣＯＯ⁻、ＣＯＮＨ_２、ＣＯＮＨＲ^２１、ＣＯＮＲ^２１Ｒ^２２、ＣＮ、ＯＨ、ＯＲ^２１、ＯＣＯＲ^２１、ＯＣＯＮＨ_２、ＯＣＯＮＨＲ^２１、ＯＣＯＮＲ^２１Ｒ^２２、ＮＯ_２、ＮＨ_２、ＮＨＲ^２１、ＮＲ^２１Ｒ^２２、ＮＨＣＯＲ^２１、ＮＲ^２１ＣＯＲ^２２、Ｎ＝ＣＨ_２、Ｎ＝ＣＨＲ^２１、Ｎ＝ＣＲ^２１Ｒ^２２、ＳＨ、ＳＲ^２１、ＳＯＲ^２１、ＳＯ_２Ｒ^２１、ＳＯ_３Ｒ^２１、ＳＯ_３Ｈ、ＳＯ_３ ^ー、ＳＯ_２ＮＨ_２、ＳＯ_２ＮＨＲ^２１若しくはＳＯ_２ＮＲ^２１Ｒ^２２で表される基である。Ｒ^２〜Ｒ^５、Ｒ^７〜Ｒ^１０、Ｒ^１２〜Ｒ^１５及びＲ^１７〜Ｒ^２０のうちの隣接する炭素原子にそれぞれ結合する基同士は、直接又は−Ｏ−、−Ｓ−、−ＮＨ−若しくは−ＮＲ^２１−を介して結合し、これらが結合する炭素原子と共に環構造を形成していてもよい。
Ｒ^２１及びＲ^２２は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数２〜１２のアルケニル基、炭素数４〜１２のシクロアルケニル基若しくは炭素数２〜１２のアルキニル基、又はこれらの基の炭素−炭素結合間に−Ｏ−、−ＮＨ−、−ＮＲ^２３−若しくは−Ｓ−が介在した基であり、このアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基及びアルキニル基が有する水素原子の一部又は全部は、ハロゲン原子、ＣＯＯＨ、ＣＯＯＲ^２３、ＣＯＯ⁻、ＣＯＮＨ_２、ＣＯＮＨＲ^２３、ＣＯＮＲ^２３Ｒ^２４、ＣＮ、＝Ｏ、ＯＨ、ＯＲ^２３、ＯＣＯＲ^２３、ＯＣＯＮＨ_２、ＯＣＯＮＨＲ^２３、ＯＣＯＮＲ^２３Ｒ^２４、＝ＮＲ^２３、ＮＨ_２、ＮＨＲ^２３、ＮＲ^２３Ｒ^２４、ＮＨＣＯＲ^２４、ＮＲ^２３ＣＯＲ^２４、Ｎ＝ＣＨ_２、Ｎ＝ＣＨＲ^２３、Ｎ＝ＣＲ^２３Ｒ^２４、ＳＨ、ＳＲ^２３、ＳＯＲ^２３、ＳＯ_２Ｒ^２３、ＳＯ_３Ｒ^２３、ＳＯ_３Ｈ、ＳＯ_３ ^ー、ＳＯ_２ＮＨ_２、ＳＯ_２ＮＨＲ^２３若しくはＳＯ_２ＮＲ^２３Ｒ^２４で表される基、炭素数７〜１２のアラルキル基、炭素数１〜１１のヘテロアリール基又は炭素数６〜１２のアリール基で置換されていてもよい。上記アラルキル基、ヘテロアリール基及びアリール基が有する水素原子の一部又は全部は、ハロゲン原子、又はＣＯＯＨ、ＣＯＯＲ^２３、ＣＯＯ⁻、ＣＯＮＨ_２、ＣＯＮＨＲ^２３、ＣＯＮＲ^２３Ｒ^２４、ＣＮ、ＯＨ、ＯＲ^２３、ＯＣＯＲ^２３、ＯＣＯＮＨ_２、ＯＣＯＮＨＲ^２３、ＯＣＯＮＲ^２３Ｒ^２４、ＮＯ_２、ＮＨ_２、ＮＨＲ^２３、ＮＲ^２３Ｒ^２４、ＮＨＣＯＲ^２４、ＮＲ^２３ＣＯＲ^２４、Ｎ＝ＣＨ_２、Ｎ＝ＣＨＲ^２３、Ｎ＝ＣＲ^２３Ｒ^２４、ＳＨ、ＳＲ^２３、ＳＯＲ^２３、ＳＯ_２Ｒ^２３、ＳＯ_３Ｒ^２３、ＳＯ_３Ｈ、ＳＯ_３ ^ー、ＳＯ_２ＮＨ_２、ＳＯ_２ＮＨＲ^２３若しくはＳＯ_２ＮＲ^２３Ｒ^２４で表される基で置換されていてもよい。
Ｒ^２３及びＲ^２４は、それぞれ独立して、炭素数１〜６のアルキル基、ベンジル基又はフェニル基であり、Ｒ^２３とＲ^２４とは、直接又は−Ｏ−、−Ｓ−、−ＮＨ−若しくは−ＮＲ^２５−を介して結合し、これらが結合する原子と共に環構造を形成していてもよい。
Ｒ^２５は、１価の有機基である。） The colorant is preferably at least one of a colorant represented by the following formula (4) and a colorant represented by the following formula (5).

(In Formula (4) and Formula (5), R < ¹ >, R < ⁶ >, R < ¹¹ > and R <^16> are respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or C1-C6. Of the fluorinated alkyl group.
R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ¹⁵ and R ^{17 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, or R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH _2. , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , OCOR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²¹ , NR ²¹ COR _{^{22, N = CH 2, N}} = CHR 21, N = CR 21 R 22, SH, SR 21, SOR 21, SO 2 R 21, SO 3 R 21, SO 3 H, SO 3 ^over, _SO 2 _NH 2, It is a group represented by SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² . The groups bonded to adjacent carbon atoms among R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ^15, and R ^{17 to} R ²⁰ are each directly or —O—, —S—, —NH. They may be bonded via — or —NR ²¹ —, and may form a ring structure together with the carbon atom to which they are bonded.
R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 12 carbon atoms, or An alkynyl group having 2 to 12 carbon atoms, or a group in which —O—, —NH—, —NR ²³ — or —S— is interposed between carbon-carbon bonds of these groups, and this alkyl group, cycloalkyl group , An alkenyl group, a cycloalkenyl group, and an alkynyl group have a part or all of a halogen atom, COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, ═O, OH, OR ²³ , OCOR ²³ , OCONH ₂ , OCONHR ²³ , OCONR ²³ R ²⁴ , ═NR ²³ , NH ₂ , NHR ²³ , NR ²³ R ²⁴ , NHCOR ²⁴ , NR ²³ COR ²⁴ , N = CH ₂ , N = CHR ²³ , N = CR ²³ R ²⁴ , SH, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H , SO _{3 ^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 group represented by ^{R 24,} aralkyl group having 7 to 12 carbon atoms, 6 to a heteroaryl group or a carbon number of 1 to 11 carbon atoms It may be substituted with 12 aryl groups. Part or all of the hydrogen atoms of the aralkyl group, heteroaryl group, and aryl group are a halogen atom, or COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, OH, OR ^{23. _{, OCOR 23, OCONH 2, OCONHR}} 23, OCONR 23 R 24, NO 2, NH 2, NHR 23, NR 23 R 24, NHCOR 24, NR 23 COR 24, N = CH 2, N = CHR 23, N = CR ²³ R ^{24, SH,} represented by _{^{SR 23, SOR 23, SO 2}} R 23, SO 3 R 23, SO 3 H, SO 3 _{^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 ^{R 24} It may be substituted with a group.
R ²³ and R ²⁴ are each independently an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group, and R ²³ and R ²⁴ may be directly or —O—, —S—, —NH—. Or it couple | bonds through -NR < ²⁵ >-and you may form the ring structure with the atom which these couple | bond.
R ²⁵ is a monovalent organic group. )

  It is preferable that the polymer has a cyclic ether group, a (meth) acryloyl group, a vinyl group, or a combination thereof.

（式（６）中、２つのＲ^１Ａは、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数４〜２０のシクロアルキル基、炭素数１〜６のハロアルキル基、２−フリル基、２−フルフリル基、２−チエニル基、２−テニル基、フェニル基又はナフチル基であり、このフェニル基又はナフチル基の水素原子の一部又は全部は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又はハロゲン原子で置換されていてもよい。
Ｒ^２Ａ及びＲ^３Ａは、それぞれ独立して、炭素数１〜１２のアルキル基又は炭素数３〜１０のシクロアルキル基である。
Ｒ^４Ａは、水素原子、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲン原子、２−フリル基、２−フルフリル基、２−チエニル基又は２−テニル基である。
Ｒ^５Ａは、スルホ基、又はＳＯ_２Ｒ^６Ａ、Ｐ（Ｒ^７Ａ）_２、ＰＯ（Ｒ^８Ａ）_２若しくはＳｉ（Ｒ^９Ａ）_３で表される基である。
Ｒ^６Ａは、水素原子、メチル基、炭素数２〜１２のアルキル基、フェニル基、又はナフチル基であり、上記炭素数２〜１２のアルキル基の水素原子の一部又は全部は、カルボキシ基、メトキシカルボニル基、エトキシカルボニル基、炭素数１〜６のアシロキシ基、ベンゾイルオキシ基又は炭素数１〜２０のアシル基で置換されていてもよく、上記フェニル基又はナフチル基の水素原子の一部又は全部は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又はハロゲン原子で置換されていてもよい。
Ｒ^７Ａ、Ｒ^８Ａ及びＲ^９Ａは、それぞれ独立して、炭素数１〜１２のアルキル基、フェニル基又はナフチル基であり、このフェニル基又はナフチル基の水素原子の一部又は全部は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又はハロゲン原子で置換されていてもよい。） The photopolymerization initiator is preferably a photopolymerization initiator represented by the following formula (6).

(In formula (6), two R ^{1A s} are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a 2-furyl group. , 2-furfuryl group, 2-thienyl group, 2-thenyl group, phenyl group or naphthyl group, part or all of the hydrogen atoms of the phenyl group or naphthyl group are alkyl groups having 1 to 6 carbon atoms, carbon It may be substituted with an alkoxy group of 1 to 6 or a halogen atom.
R ^2A and R ^3A are each independently an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
R ^4A is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a 2-furyl group, a 2-furfuryl group, a 2-thienyl group, or a 2-thenyl group.
R ^5A is a sulfo group or a group represented by SO ₂ R ^6A , P (R ^7A ) ₂ , PO (R ^8A ) ₂ or Si (R ^9A ) ₃ .
R ^6A is a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms are a carboxy group, A methoxycarbonyl group, an ethoxycarbonyl group, an acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group, or an acyl group having 1 to 20 carbon atoms may be substituted, or a part of hydrogen atoms of the phenyl group or naphthyl group or All may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
R ^7A , R ^8A and R ^9A are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or naphthyl group have a carbon number It may be substituted with a 1-6 alkyl group, a C1-C6 alkoxy group or a halogen atom. )

  The radiation-sensitive colored composition is suitable for forming a colored pattern of a liquid crystal display element.

  Another invention made in order to solve the above-mentioned problems is the step of forming a coating film on a substrate using the radiation-sensitive colored composition, the step of irradiating a part of the coating film, and the radiation It is a coloring pattern formation method provided with the process of developing the irradiated coating film, and the process of heating the said developed coating film.

  Yet another invention made to solve the above problems is a colored pattern formed from the radiation-sensitive colored composition, and a liquid crystal display device comprising the colored pattern.

  The radiation-sensitive colored composition of the present invention can form a colored pattern in which contamination of the liquid crystal layer by the colorant is reduced. In the colored pattern and the liquid crystal display element of the present invention, the contamination of the liquid crystal layer by the colorant is reduced, and the colored pattern forming method of the present invention can form such a colored pattern.

<Radiation-sensitive coloring composition>
The radiation-sensitive colored composition contains [A] a polymer, [B] a photopolymerization initiator, and [C] a colorant.

<[A] polymer>
[A] The well-known thing normally used for a radiation sensitive composition can be used for a polymer. [A] The polymer is preferably an alkali-soluble resin having an acidic group such as a carboxy group or a phenolic hydroxyl group, and more preferably a resin having a carboxy group, from the viewpoint of developability to an alkaline developer. preferable.

(Copolymer (α))
Examples of the resin having a carboxy group include (a1) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a combination thereof (hereinafter referred to as “compound (a1)”), and (a2) an unsaturated group other than (a1). A copolymer (α) with a compound (hereinafter referred to as “compound (a2)”) is preferred.

Specific examples of the compound (a1) include
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

  In the copolymer (α), the compound (a1) can be used alone or in admixture of two or more. In the copolymer (α), the lower limit of the content of the structural unit derived from the compound (a1) is preferably 5% by mass, more preferably 7% by mass, and still more preferably 10% by mass. On the other hand, the upper limit is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. By setting the content of the structural unit derived from the compound (a1) within such a range, a radiation-sensitive colored composition in which various properties such as radiation sensitivity and developability are balanced at a higher level can be obtained.

Specific examples of the compound (a2) include
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Methacrylic acid hydroxyalkyl esters such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate and diethyl fumarate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methoxystyrene;
Conjugated diene compounds such as 1,3-butadiene and isoprene;
(Meth) acrylic acid ester having a cyclic ether group or vinyl group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl (meth) acrylate;
Other examples include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

  In the copolymer (α), the compound (a2) can be used alone or in admixture of two or more. In the copolymer (α), the lower limit of the content of the structural unit derived from the compound (a2) is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass. On the other hand, the upper limit is preferably 70% by mass, more preferably 60% by mass, and even more preferably 50% by mass. By setting the content of the structural unit of the compound (a2) in this range, the molecular weight of the copolymer can be easily controlled, and the radiation-sensitive coloring composition in which developability, radiation sensitivity, etc. are balanced at a higher level. A thing is obtained.

  The copolymer (α) can be produced by a known method. For example, according to the methods disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 07/029871, etc., the structure, Mw (weight average molecular weight), Mn (number average molecular weight), Mw / Mn and the like can also be controlled.

  [A] (meth) acrylic acid ester having cyclic ether groups such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate with respect to the carboxy group of copolymer (α) as the polymer A copolymer having a (meth) acryloyl group introduced therein can be used. Examples of such copolymers include JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, Examples thereof include polymers described in JP-A-2008-181095.

(Cardo resin)
[A] It is also preferable to use a cardo resin as the polymer. As such [A] polymer, a polymer obtained by reacting a compound having a fluorene skeleton represented by the following formula (7) with tetrabasic dianhydride is represented by the following formula (8). And a polymer obtained by adding a compound.

In formula (7), ring Z ¹ and ring Z ² are each independently a monocyclic or condensed polycyclic hydrocarbon ring. R ^1a and R ^1b are each independently a hydrogen atom or an alkyl group. R ^2a and R ^2b are each independently a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group. R ^3a and R ^3b are each independently a hydrogen atom or a methyl group. k1 and k2 are each independently an integer of 0 to 4. m1 and m2 are each independently an integer of 0 to 3. n1 and n2 are each independently an integer of 0 to 10. p1 and p2 are each independently an integer of 0 to 4. However, when ring Z ¹ and ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are each independently an integer of 1 to 3, and ring Z ¹ and ring Z ² are fused polycyclic carbon for hydrocarbon ring, the sum of p2 included in the sum and ring Z ² of p1 contained in the ring Z ¹ is respectively 1 or more.

In formula (8), R ³¹ is a hydrogen atom or a methyl group. R ³² is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. X ¹ is an epoxy group, a 3,4-epoxycyclohexyl group, or a group represented by the following formula (9-1) or formula (9-2). * Indicates a binding site.

In the above formula (7), the hydrocarbon ring represented by the ring Z ¹ and the ring Z ² is usually an aromatic ring. The hydrocarbon corresponding to this hydrocarbon ring is a monocyclic or condensed polycyclic hydrocarbon, for example, a monocyclic hydrocarbon such as benzene, a condensed bicyclic hydrocarbon (for example, carbon number 8 such as indene and naphthalene). And condensed polycyclic hydrocarbons such as condensed bicyclic hydrocarbons having a carbon number of -20, preferably condensed bicyclic hydrocarbons having 10 to 16 carbon atoms, and condensed tricyclic hydrocarbons such as anthracene and phenanthrene. It is done. Particularly preferred hydrocarbons in applications requiring high refractive index and heat resistance include condensed polycyclic aromatic hydrocarbons, and naphthalene is particularly preferred. In addition, benzene is preferred in applications that require particularly high solubility, compatibility, and low solution viscosity.

In the above formula (7), the alkyl group represented by R ^1a and R ^1b is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group. Can be mentioned. Among these, a C1-C6 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a methyl group is further more preferable. As the substitution numbers k1 and k2, 0 and 1 are preferable, and 0 is more preferable.

Examples of the hydrocarbon group represented by R ^2a and R ^2b in the formula (7) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include those exemplified as R ^{1a and the} like. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 20 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like. The cycloalkyl group is preferably a cycloalkyl group having 5 to 8 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the alkoxy group represented by R ^2a and R ^2b in the above formula (7) include C 1-12 alkoxy groups such as methoxy group, ethoxy group, and benzoxy group. Examples of the acyl group represented by R ^2a and R ^2b in the above formula (7) include C 2-13 acyl groups such as methanoyl group, ethanoyl group (acetyl group), and benzoyl group. Examples of the alkoxycarbonyl group represented by R ^2a and R ^2b in the above formula (7) include C2-C13 alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, and a benzoxycarbonyl group. Examples of the halogen atom represented by R ^2a and R ^2b in the formula (7) include a fluorine atom and a chlorine atom.

R ^2a and R ^2b are preferably hydrocarbon groups, more preferably alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, and even more preferably alkyl groups having 1 to 12 carbon atoms. The upper limit of m1 and m2 is preferably 2, more preferably 1, and even more preferably 0.

  The upper limit of the addition numbers n1 and n2 of the (poly) alkyleneoxy group in the above formula (7) is preferably 8, more preferably 6, and even more preferably 4. The lower limit can be 1. The upper limit of the sum of n1 and n2 (n1 + n2) is preferably 16, more preferably 12, and more preferably 8. This lower limit can be set to 2, for example.

  The upper limit of p1 and p2 in the above formula (7) is preferably 2. This lower limit is preferably 1, for example. The upper limit of the sum (p1 + p2) of p1 and p2 is preferably 6, and more preferably 4. This lower limit can be 2. In particular, p1 and p2 are preferably 2 and 3 in applications in which the crosslink density of the cured product is required.

  In addition, the several hydroxyl group containing group which comprises the same phenol frame | skeleton may be the same, and may differ. For example, the plurality of hydroxyl group-containing groups may be constituted by (i) a hydroxyl group alone (except when p1 and p2 are 2), where n1 = 0 (n2 = 0) (ii) n1 = 0 (n2 = 0) and a hydroxy (poly) alkoxy group (such as 2-hydroxyethoxy group) where n1 ≠ 0 (n2 ≠ 0), and (iii) n1 ≠ 0 (n2 ≠ 0) may be composed of the same hydroxy (poly) alkoxy group alone, and (iv) different hydroxy (poly) alkoxy groups with n1 ≠ 0 (n2 ≠ 0) [eg 2-hydroxy Ethoxy group and 2- (2-hydroxyethoxy) ethoxy group].

  Specific examples of the compound represented by the above formula (7) include 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes.

  Examples of 9,9-bis (hydroxyalkoxynaphthyl) fluorenes include 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy). ) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [5- (2-hydroxypropoxy) -1-naphthyl] fluorene, etc. 9,9-bis (hydroxyC2-4alkoxynaphthyl) fluorene and the like.

  Examples of 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes include 9,9-bis {6- [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl} fluorene, 9,9-bis {6 -[2- (2-hydroxypropoxy) propoxy] -2-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis And 9,9-bis (hydroxydialkoxynaphthyl) fluorenes such as {5- [2- (2-hydroxypropoxy) propoxy] -1-naphthyl} fluorene.

  Examples of the tetrabasic acid dianhydride include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride , Cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Biphenyl ether tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxo Tetrahydrofuran-3-yl) -1,2,3,4-tetrahydrona Talen-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9, Examples include 10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, and the like. Among these, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, benzophenonetetracarboxylic dianhydride And biphenyltetracarboxylic dianhydride is preferred.

  The ratio of the tetrabasic acid dianhydride to 1 mol of the compound having the fluorene skeleton in the reaction between the compound having the fluorene skeleton and the tetrabasic acid dianhydride is, for example, 0.5 mol to 1.5 mol. If it is out of this range, a sufficient molecular weight may not be obtained.

  In the reaction between the compound having a fluorene skeleton and tetrabasic dianhydride, a catalyst may be used. Examples of the catalyst include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, Tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] nonene-5 , Quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, tributylphosphine, triphenylphosphine, etc. Door can be. The amount of the catalyst to be used is not particularly limited, but is preferably 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass in total of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. If the amount of the catalyst exceeds 2.0 parts by mass, the electrical characteristics and storage stability may be adversely affected.

  In the reaction, a solvent may be used for the purpose of dissolving the reaction raw materials and reducing the viscosity. The type of solvent is not particularly limited as long as it does not inhibit the reaction. For example, glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Glycol ether acetates, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether A Tate, propylene glycol ether acetates such as dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, acetate esters such as ethyl acetate and butyl acetate, dimethyl Examples thereof include sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  The amount of the solvent to be used is not particularly limited, but a range of 25 parts by mass or more and 150 parts by mass or less is preferable with respect to 100 parts by mass in total of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

Examples of the carboxylic acid reactive (meth) acrylate represented by the above formula (8) added to the polymer obtained by the reaction of a compound having a fluorene skeleton and a tetrabasic acid dianhydride include, for example, glycidyl (meth) acrylate. 3,4-epoxycyclohexyl (meth) acrylate, (meth) acrylic acid [3,4-epoxytricyclo (5.2.1.0 ^2,6 ) decan-9-yl], and the like.

  In the reaction between the polymer and the carboxylic acid reactive (meth) acrylate compound, a catalyst may be used for the purpose of promoting the reaction. Examples of the catalyst include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris. (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] nonene-5, And the like, quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, tributylphosphine, triphenylphosphine, etc. Compounds, and the like.

  In reacting the carboxylic acid reactive (meth) acrylate, it is preferable to add a polymerization inhibitor. The polymerization inhibitor is not particularly limited as long as it suppresses the unsaturated bond reaction. For example, hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl And piperidine-1-oxyl.

(Other configurations)
[A] The polymer is not limited to the above-described copolymer (α) or cardo resin.

  [A] The polymer is preferably a polymer having a polymerizable group such as a cyclic ether group, a (meth) acryloyl group, a vinyl group, or a combination thereof. Examples of the cyclic ether group include an oxiranyl group and an oxetanyl group. By using a polymer having such a polymerizable group, elution of the [C] colorant in the colored pattern obtained from the radiation-sensitive colored composition can be reduced. As such [A] polymer, (1) a (meth) acryloyl group or the like is introduced by using a carboxylic acid-reactive (meth) acrylate or the like to the copolymer (α) or cardo resin described above. A copolymer obtained by using the above-mentioned cyclic ether group or (meth) acrylic acid ester having a vinyl group as the compound (a2) in the copolymer (α), and other ( 3) An epoxy resin having a polymerizable group such as an epoxy acrylate resin can be used. As the epoxy acrylate resin, an acid-modified alkali-soluble resin is preferably used.

  [A] As a minimum of the content rate of the structural unit which has a polymeric group in a polymer, 5 mass% is preferable and 10 mass% is more preferable. On the other hand, as this upper limit, 50 mass% is preferable and 40 mass% is more preferable. By setting the content of the structural unit having a polymerizable group in such a range, elution of the colorant can be effectively reduced while sufficiently providing developability and the like.

  [A] The lower limit of the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the polymer is usually 1,000, preferably 3,000. The upper limit is usually 100,000, preferably 50,000. [A] The upper limit of the ratio (Mw / Mn) of the weight average molecular weight (Mw) of the polymer and the number average molecular weight (Mn) in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is usually 5 And 3 is preferred.

  [A] A polymer can be used individually or in mixture of 2 or more types.

<[B] Photopolymerization initiator>
[B] The photopolymerization initiator has two or more sites represented by the above formula (1) in one molecule. [B] Since the photopolymerization initiator has a plurality of the above-mentioned sites, it can form a colored pattern with excellent radiation sensitivity and suppressed elution of the [C] colorant.

The monovalent organic group represented by R ^X in Formula (1) is not particularly limited as long as it is a group containing one or more carbon atoms, but is a hydrocarbon group such as an alkyl group or a cycloalkyl group, a haloalkyl group, A 2-furyl group, a 2-furfuryl group, a 2-thienyl group, a 2-thenyl group, a phenyl group, a naphthyl group, a group formed by combining these, and the like can be given. Part or all of the hydrogen atoms of the phenyl group or naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.

Examples of the alkyl group represented by R ^X include those exemplified as the alkyl group represented by R ^{1a and the} like, preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred.

Examples of the cycloalkyl group represented by R ^X include those exemplified as the cycloalkyl group represented by R ^{2a and the} like, and a cycloalkyl group having 4 to 20 carbon atoms is preferable.

The haloalkyl group represented by R ^X is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, such as a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, and a chlorohexyl group. Mention may be made of haloalkyl groups having 1 to 6 carbon atoms.

  [B] As the photopolymerization initiator, those represented by the above formula (6) are preferable. By using a compound having such a structure, the sensitivity can be increased and the solubility and the like can be increased.

In formula (6), a plurality of R ^1A are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a 2-furyl group, 2-furfuryl group, 2-thienyl group, 2-thenyl group, phenyl group or naphthyl group, and part or all of the hydrogen atoms of the phenyl group or naphthyl group are alkyl groups having 1 to 6 carbon atoms, carbon number It may be substituted with 1 to 6 alkoxy groups or halogen atoms.
R ^2A and R ^3A are each independently an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
R ^4A is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a 2-furyl group, a 2-furfuryl group, a 2-thienyl group, or a 2-thenyl group.
R ^5A is a sulfo group or a group represented by —SO ₂ R ^6A , —P (R ^7A ) ₂ , —PO (R ^8A ) _2, or —Si (R ^9A ) ₃ .
R ^6A is a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms are a carboxy group, A methoxycarbonyl group, an ethoxycarbonyl group, an acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group, or an acyl group having 1 to 20 carbon atoms may be substituted, or a part of hydrogen atoms of the phenyl group or naphthyl group or All may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
R ^7A , R ^8A and R ^9A are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or naphthyl group have a carbon number It may be substituted with a 1-6 alkyl group, a C1-C6 alkoxy group or a halogen atom.

Specific examples of each group represented by R ^1A include those exemplified as the group represented by R ^X. R ^1A is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms represented as R ^2A and R ^3A include those exemplified as the groups represented as R ^1a , R ^{2a and the} like. . R ^2A and R ^3A are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms represented as R ^4A include those exemplified as the groups represented as R ^1a , R ^{2a and the} like. R ^4A is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the alkyl group having 2 to 12 carbon atoms represented as R ^6A include those exemplified as the group represented as R ^{1a and the} like. As a C1-C6 acyloxy group which is a substituent, an acetoxy group, a propionyloxy group, etc. are mentioned, for example. As a C1-C20 acyl group which is a substituent, a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group etc. are mentioned, for example.

Examples of the alkyl group having 1 to 12 carbon atoms represented as R ^7A , R ^8A and R ^9A include those exemplified as the group represented as R ^{1a and the} like. Examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms which are substituents include those exemplified as the groups represented by R ^1a , R ^{2a and the} like.

R ^5A is preferably a group represented by SO ₂ R ^6A . R ^6A is preferably an alkyl group having 2 to 12 carbon atoms in which part or all of the hydrogen atoms are substituted with an acyloxy group having 1 to 6 carbon atoms.

R ^1A , R ^2A , R ^3A and R ^4A are each an alkyl group having 1 to 8 carbon atoms, and R ^5A is SO ₂ R ^6A , PO (R ^8A ) ₂ or Si (R ^9A ) ₃ . Wherein R ^6A is an alkyl group having 2 to 6 carbon atoms in which a part or all of hydrogen atoms are substituted with an acetoxy group, R ^8A is a phenyl group, and R ^9A is It is preferable that it is a C1-C6 alkyl group. With such a structure, the solubility can be further improved.

  The compound represented by the above formula (6) can be obtained, for example, by the production method described in JP-A-2011-177876.

  The content of [B] photopolymerization initiator in the radiation-sensitive colored composition is not particularly limited, but the lower limit is preferably, for example, 5 parts by mass with respect to 100 parts by mass of [A] polymer (solid content). 10 parts by mass is more preferable. On the other hand, as this upper limit, 50 mass parts is preferable and 30 mass parts is more preferable.

<[B ′] Photopolymerization Initiator>
The said radiation sensitive coloring composition can contain [B '] other photoinitiators with a [B] photoinitiator. [B ′] Photopolymerization initiators include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  The total content of [B] photopolymerization initiator and [B ′] photopolymerization initiator in the radiation-sensitive colored composition is not particularly limited, but the lower limit is, for example, [A] polymer (solid content) 100. 5 mass parts is preferable with respect to mass parts, and 10 mass parts is more preferable. On the other hand, as this upper limit, 50 mass parts is preferable and 30 mass parts is more preferable.

<[C] Colorant>
[C] The colorant is a colorant having a lactam structure, this isomer ring structure, or a combination thereof. The lactam structure is an aliphatic hydrocarbon ring structure containing a group represented by -CONR- (R is a hydrogen atom or an organic group). Examples of the isomer ring structure of the lactam structure include an aliphatic ring structure in which —CO— and —NR— (R is a hydrogen atom or an organic group) are bonded via a carbon atom. .

  [C] The colorant is not particularly limited as long as it has a lactam structure, this isomer ring structure, or a combination thereof, but it is represented by the site represented by the above formula (2) and the above formula (3). It is preferable to have at least one of the sites. A substituent may be bonded to the benzene ring in the above formulas (2) and (3). Examples of such a colorant include a bis-oxodihydroindoleylene-benzodifuranone colorant having a structure in which two of the above-mentioned sites are substituted on the benzodifuranone skeleton, and its isomers or tautomers.

  [C] The colorant is preferably at least one of the colorant represented by the above formula (4) and the colorant represented by the above formula (5).

In formula (4) and formula (5), R ¹ , R ⁶ , R ¹¹ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents a fluorinated alkyl group.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ⁶ , R ¹¹ and R ¹⁶ include those exemplified as the alkyl group represented by R ^{1a and the} like. Examples of the fluorinated alkyl group include groups in which some or all of hydrogen atoms of these alkyl groups are substituted with fluorine atoms.

R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ¹⁵ and R ^{17 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, or R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH _2. , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , OCOR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²¹ , NR ²¹ COR ²² , N = CH ₂ , N = CHR ²¹ , N = CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , It is a group represented by SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² . The groups bonded to adjacent carbon atoms among R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ^15, and R ^{17 to} R ²⁰ are each directly or —O—, —S—, —NH. They may be bonded via — or —NR ²¹ —, and may form a ring structure together with the carbon atom to which they are bonded.

R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 12 carbon atoms, or An alkynyl group having 2 to 12 carbon atoms, or a group in which —O—, —NH—, —NR ²³ — or —S— is interposed between carbon-carbon bonds of these groups, and this alkyl group, cycloalkyl group , An alkenyl group, a cycloalkenyl group, and an alkynyl group have a part or all of a halogen atom, COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, ═O, OH, OR ²³ , OCOR ²³ , OCONH ₂ , OCONHR ²³ , OCONR ²³ R ²⁴ , ═NR ²³ , NH ₂ , NHR ²³ , NR ²³ R ²⁴ , NHCOR ²⁴ , NR ²³ COR ²⁴ , N = CH ₂ , N = CHR ²³ , N = CR ²³ R ²⁴ , SH, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H , SO _{3 ^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 group represented by ^{R 24,} aralkyl group having 7 to 12 carbon atoms, 6 to a heteroaryl group or a carbon number of 1 to 11 carbon atoms It may be substituted with 12 aryl groups. Part or all of the hydrogen atoms of the aralkyl group, heteroaryl group, and aryl group are a halogen atom, or COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, OH, OR ^{23. _{, OCOR 23, OCONH 2, OCCNHR}} 23, OCONR 23 R 24, NO 2, NH 2, NHR 23, NR 23 R 24, NHCOR 24, NR 23 COR 24, N = CH 2, N = CHR 23, N = CR ²³ R ^{24, SH,} represented by _{^{SR 23, SOR 23, SO 2}} R 23, SO 3 R 23, SO 3 H, SO 3 _{^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 ^{R 24} It may be substituted with a group.

Note that ═O and ═NR ²³ indicate that two hydrogen atoms bonded to one carbon atom are substituted with O or NR ²³ .

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{2 to} R ¹⁰ and R ¹² to ²⁰ include those exemplified as the alkyl group represented as R ^{1a and the} like. Examples of the cycloalkyl group having 3 to 12 carbon atoms include those exemplified as the cycloalkyl group represented by R ^{2a and the} like. Examples of the alkenyl group having 2 to 12 carbon atoms include an ethenyl group (vinyl group) and a propenyl group (allyl group). Examples of the C 4-12 cycloalkenyl group include a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, and the like. Examples of the alkynyl group having 2 to 12 carbon atoms include ethynyl group and propynyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and phenethyl group. Examples of the heteroaryl group having 1 to 11 carbon atoms include groups having an aromatic ring having 5 to 12 ring members such as a thiophene ring, a pyrrole ring, and a furan ring. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

R ²³ and R ²⁴ are each independently an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group, and R ²³ and R ²⁴ may be directly or —O—, —S—, —NH—. Or it couple | bonds through -NR < ²⁵ >-and you may form the ring structure with the atom which these couple | bond.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²³ and R ²⁴ include those exemplified as the alkyl group represented by R ^{1a and the} like.

R ²⁵ is a monovalent organic group. Examples of the monovalent organic group include those exemplified as the monovalent organic group represented by R ^X.

  When the colorant represented by the above formula (4) and the colorant represented by the above formula (5) are anionic, they exist as an ionic compound together with a cation. The cations to be paired are not particularly limited, and examples thereof include alkali metal ions such as sodium ions, other metal ions, ammonium ions, and organic metal ions.

R ¹ , R ² , R ^{4 to} R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{14 to} R ¹⁷ , R ¹⁹ , R ²⁰ are preferably a hydrogen atom, a fluorine atom and a chlorine atom. Atoms are more preferred. R ³ , R ⁸ , R ¹³ and R ¹⁸ are hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N _{(CH 3) (C 2 H} 5), N (C 2 H 5) 2, α- naphthyl, beta-naphthyl and SO ₃ ^over is preferred. R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , R ⁵ and R ¹⁰ , R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ And R ¹⁹ , R ¹⁵ and R ²⁰ are preferably the same.

  The colorant represented by the above formula (4) and the colorant represented by the above formula (5) can be produced, for example, by the method described in WO2000 / 24736.

  [C] The colorant usually functions as a black pigment (colorant). [C] The upper limit of the particle size of the colorant is preferably 0.4 μm, and more preferably 0.3 μm. On the other hand, the lower limit is, for example, 0.01 μm. By using the [C] colorant having such a particle size, the dispersion stability of the [C] colorant in the radiation-sensitive colored composition is improved.

  [C] The content of the colorant is not particularly limited, but is preferably 5 parts by weight, more preferably 10 parts by weight, and 20 parts by weight as a lower limit for 100 parts by weight of the solid content in the radiation-sensitive colored composition. Further preferred. On the other hand, as this upper limit, 60 mass parts is preferable, 50 mass parts is more preferable, and 40 mass parts is further more preferable. [C] By setting the content of the colorant in such a range, a sufficiently colored pattern can be obtained while suppressing elution of the colorant.

<[C '] Other colorant>
In the radiation-sensitive colored composition, [C ′] other colorants other than the [C] colorant can be used in combination for the purpose of adjusting the color tone. [C ′] Examples of other colorants include known pigments and dyes.

  The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Specific examples include those with the following color index (CI) names.

  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 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
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 inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, Examples include cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  The dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like, for example, those having the following color index (CI) names. Can be mentioned.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;

C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.
[C ′] Other colorants may be used alone or in admixture of two or more.

  The total content of the [C] colorant and [C ′] other colorant in the radiation-sensitive colored composition is preferably 5 parts by mass, more preferably 10 parts by mass, as the lower limit for the total solid content. Part by mass is more preferable. On the other hand, as this upper limit, 60 mass parts is preferable, 50 mass parts is more preferable, and 40 mass parts is further more preferable. By setting the total content of the colorant in such a range, a sufficiently colored pattern can be obtained while suppressing elution of the colorant.

<Other optional components>
The radiation-sensitive coloring composition is a thiol-based compound, a polyfunctional acrylate, a compound having a cyclic ether group, a surfactant, an adhesion assistant, a dispersing agent, a dispersion as long as the effects of the present invention are not impaired. You may contain other arbitrary components, such as an adjuvant and a solvent. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<Thiol compound>
A thiol compound is a compound having a thiol group (mercapto group). As the thiol compound, a compound having two or more mercapto groups in one molecule is preferable. An example of such a compound is a compound represented by the following formula (10).

In Formula (10), R ³³ is a methylene group or an alkylene group having 2 to 10 carbon atoms. However, some or all of the hydrogen atoms contained in these groups may be substituted with alkyl groups. Y ¹ is a single bond, —CO— or —O—CO— *. However, bond binds to ^{R 33} marked with *. n is an integer of 2-10. A ¹ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or a group represented by the following formula (11) when n is 3. It is.

In the formula ^{(11), R} 34 ~R ³⁶ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms. “*” Is a bond.

  A typical example of the compound represented by the formula (10) is an esterified product of mercaptocarboxylic acid and a polyhydric alcohol. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, pentaerythritol and the like.

  Examples of the compound represented by the formula (10) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptopentylate) and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Is preferred.

  As the thiol compound having two or more mercapto groups in one molecule, a compound represented by the following formula (12) or formula (13) can also be used.

In the above formula ^{(12), R 41} is an alkylene group of methylene group or 2 to 20 carbon atoms. ^R42 is a methylene group or an alkylene group having 2 to 6 carbon atoms. k is an integer of 1-20.

In the above formula (13), R ^{43 to} R ⁴⁶ are each independently a hydrogen atom, a hydroxyl group or a group represented by the following formula (14). However, at least one of R ^{43 to} R ⁴⁶ is a group represented by the following formula (14).

In the above formula ^{(14), R 47} is a methylene group or an alkylene group having 2 to 6 carbon atoms.

  The thiol compound can be used by mixing one or more compounds. As a minimum of content of a thiol system compound in the radiation sensitive coloring composition, 0.5 mass part is preferred to 100 mass parts of [A] polymer, and 1 mass part is more preferred. On the other hand, as this upper limit, 20 mass parts is preferable and 15 mass parts is more preferable. When the content of the thiol compound is less than the above lower limit, the effect of improving the curability is not sufficiently obtained, and when it exceeds the above upper limit, the pattern shape may be impaired.

<Multifunctional acrylate>
By containing a polyfunctional acrylate in the radiation-sensitive colored composition, the hardness of the resulting pattern can be increased. Polyfunctional acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly ( ) Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional acrylates can be used alone or in combination of two or more.

  As a minimum of content of polyfunctional acrylate, 10 mass parts are preferred to 100 mass parts of [A] polymer, and 30 mass parts are more preferred. On the other hand, as this upper limit, 200 mass parts is preferable and 150 mass parts is more preferable. By setting the polyfunctional acrylate content in such a range, the hardness of the resulting pattern can be further increased, and the radiation sensitivity of the radiation-sensitive colored composition can be increased.

<Compound having a cyclic ether group>
The compound having a cyclic ether group is a compound having a cyclic ether group and other than the [A] polymer (for example, a low molecular weight compound having a molecular weight of 1,000 or less). The radiation-sensitive colored composition contains a compound having a cyclic ether group, thereby promoting the crosslinking of the [A] polymer and the like, and further increasing the hardness of the resulting pattern. The radiation sensitivity of the coloring composition can be increased.

  The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxiranyl group, oxetanyl group, etc.) in the molecule.

Examples of the compound having two or more oxiranyl groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Bisphenol type diglycidyl ethers such as hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil. These compounds having a cyclic ether group may be used alone or in combination of two or more.

  Examples of the compound having a cyclic ether group having two or more oxetanyl groups in the molecule include bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4-bis [(3-ethyloxetane- 3-yl) methoxymethyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl) methyl] ether (also known as bis (3- Ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] Bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl- -Oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3- Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3- Oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, xylenebisoxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3 Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3) -Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl) -3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis ( 3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. Can be mentioned.

  As a minimum of content of a compound which has a cyclic ether group, 0.5 mass part is preferred to 100 mass parts of [A] polymers, 1 mass part is more preferred, and 10 mass parts is still more preferred. On the other hand, the upper limit is usually 150 parts by mass, preferably 100 parts by mass, more preferably 50 parts by mass, and even more preferably 25 parts by mass. By making content of the compound which has a cyclic ether group into the said range, the hardness of the pattern obtained can be raised more.

<Surfactant>
Surfactant is a component which improves the film-forming property of the said radiation sensitive coloring composition. By containing the surfactant, the radiation-sensitive colored composition can improve the surface smoothness of the coating film, and as a result, improve the film thickness uniformity of the resulting pattern (cured film).

  Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. These surfactants may be used alone or in combination of two or more.

  The lower limit of the surfactant content is preferably 0.01 parts by mass and more preferably 0.05 parts by mass with respect to 100 parts by mass of the [A] polymer. On the other hand, the upper limit is usually 3 parts by mass, preferably 2 parts by mass, and more preferably 1 part by mass. By making content of surfactant into the said range, the film thickness uniformity of the coating film formed can be improved more.

<Adhesion aid>
The adhesion aid is a component that improves the adhesion between the pattern forming object such as a substrate and the pattern (cured film). The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum.

  As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group. These adhesion assistants may be used alone or in combination of two or more. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among these, as the functional silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, And γ-methacryloxypropyltrimethoxysilane are preferred.

  As a minimum of content of adhesion assistant, 0.5 mass part is preferred to 100 mass parts of [A] polymer, and 1 mass part is more preferred. On the other hand, the upper limit is usually 30 parts by mass, preferably 20 parts by mass, and more preferably 10 parts by mass. By setting the content of the adhesion aid in the above range, the adhesion between the formed pattern and the substrate is further improved.

<Dispersant>
By using the dispersant and the dispersion aid described below, the dispersibility stability of the [C] colorant and the like can be improved. As the dispersant, for example, an appropriate dispersant such as a cation system, an anion system, or a nonionic system can be used, and a polymer dispersant is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant can be obtained commercially. For example, as an acrylic copolymer, “Disperbyk-2000”, “Disperbyk-2001”, “BYK-LPN6919”, “BYK” manufactured by BYK Co., Ltd. -LPN21116 ", as polyurethane," Disperbyk-161 "," Disperbyk-162 "," Disperbyk-165 "," Disperbyk-167 "," Disperbyk-170 "," Disperbyk-182 ", manufactured by BYK Lubrizol "Solsperse 76500", polyethyleneimine, Lubrizol "Solsperse 24000", polyester, Ajinomoto Finetechno "Ajisper PB821" AJISPER PB822 ", mention may be made of the" Ajisper PB880 "and the like.

  These dispersants can be used alone or in admixture of two or more.

  As a minimum of content of a dispersing agent, 1 mass part is preferred to 100 mass parts of [C] coloring agent (solid content), and 10 mass parts is more preferred. On the other hand, the upper limit is usually 100 parts by mass, preferably 70 parts by mass, and more preferably 50 parts by mass. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

<Dispersing aid>
Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

<Method for preparing radiation-sensitive colored composition>
The radiation-sensitive colored composition is usually dissolved or dispersed by mixing [A] polymer, [B] photopolymerization initiator, [C] colorant, and other optional components as necessary in a solvent. To be prepared. In addition, after preparing the dispersion liquid containing [C] a coloring agent, a dispersing agent, a solvent (dispersion medium), etc., you may prepare by mixing this dispersion liquid with another component.

<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses each component in the radiation-sensitive colored composition and does not react with each component is preferably used. Such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatics Examples include hydrocarbons, ketones, and other esters. As the solvent, the solvents described in JP2011-232632 can be used.

<Method for forming colored pattern>
The radiation-sensitive colored composition is preferable for forming a liquid crystal display element pattern (cured film). In addition, the present invention suitably includes a colored pattern formed from the radiation-sensitive colored composition.

The colored pattern forming method of the present invention is
(1) A step of forming a coating film on a substrate using the radiation-sensitive colored composition,
(2) A step of irradiating a part of the coating film with radiation,
(3) A step of developing the coating film irradiated with the radiation, and (4) a step of heating the developed coating film.

  According to the forming method of the present invention, it is possible to form a colored pattern for a display element in which contamination of the liquid crystal layer is suppressed and the voltage holding ratio is excellent. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating film of the radiation-sensitive colored composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Etc.

  When a coating film is formed by a coating method, the coating film is preferably formed by heating (prebaking) the coated surface after applying the radiation-sensitive colored composition solution on the transparent conductive film. Can do. As solid content concentration of the composition solution used for the apply | coating method, 5 to 50 mass% is preferable. As a coating method of the radiation sensitive coloring composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, an ink jet coating method, etc. This method can be adopted. Of these, spin coating and slit coating are preferred.

  The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., but are about 70 ° C. or higher and 120 ° C. or lower and 1 minute or longer and 15 minutes or shorter. The average film thickness after pre-baking of the coating film is preferably 0.5 μm or more and 10 μm or less.

[Step (2)]
In this step, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Among these, radiation having a wavelength in the range of 250 nm or more and 550 nm or less is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

The lower limit of the radiation dose (exposure dose) is preferably 100 J / m ² as a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), and 200 J / m ² is preferable. ² is more preferable. As this upper limit, 5,000 J / m ² is preferable, and 3,000 J / m ² is more preferable.

[Step (3)]
In this step, the coated film after irradiation is developed to remove unnecessary portions and form a predetermined pattern. Examples of the developer used for development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is done. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.

  As a developing method, any of a liquid filling method, a dipping method, a shower method, and the like may be used, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, after washing with running water for about 30 seconds to 90 seconds, a desired pattern can be obtained by air drying with compressed air or compressed nitrogen.

[Step (4)]
In this step, the obtained patterned coating film is heated with a suitable heating device such as a hot plate or oven to obtain a cured film for display element (colored pattern). The heating temperature is about 100 ° C. or higher and 250 ° C. or lower. The heating time is, for example, about 5 minutes to 30 minutes on a hot plate and about 20 minutes to 180 minutes or less on an oven.

<Method for manufacturing display element>
The liquid crystal display element provided with the said coloring pattern is also suitably contained in this invention. As a method for producing a liquid crystal display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive colored composition is formed on the transparent conductive film of one of the substrates. Using the product, a spacer or a protective film or both are formed according to the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal serving as a liquid crystal layer is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling holes are sealed to form a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Is obtained.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film or spacer, and an alignment film are formed are prepared in the same manner as described above. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then a liquid crystal serving as a liquid crystal layer is dropped into a liquid droplet using a liquid crystal dispenser. Paste. Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the liquid crystal display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, the H film itself The polarizing plate which consists of, etc. are mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The weight average molecular weight (Mw) of the polymer was measured by the following method.

[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Synthesis of polymer>
[Synthesis Example 1] (A-1) Synthesis of alkali-soluble resin having methacryloyl group in side chain In flask equipped with cooling tube and stirrer, 4 parts by mass of 2,2′-azobisisobutyronitrile and diethylene glycol methyl Charge 300 parts by weight of ethyl ether, 23 parts by weight of methacrylic acid, 10 parts by weight of styrene, 32 parts by weight of benzyl methacrylate and 35 parts by weight of methyl methacrylate, and 2.7 parts by weight of α-methylstyrene dimer as a molecular weight regulator. Prepared. Next, while gently stirring, the temperature of the solution is raised to 80 ° C., and this temperature is maintained for 4 hours, then the temperature is increased to 100 ° C., and this temperature is maintained for 1 hour to carry out the polymerization to contain a copolymer. Solution was obtained (solid concentration = 24.9% by mass). Mw of the obtained copolymer was 12,500. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and after stirring at 90 ° C. for 30 minutes in an air atmosphere, methacrylic acid was added. A copolymer (A-1) was obtained by adding 16 parts by mass of glycidyl and reacting at 90 ° C. for 10 hours (solid content concentration = 29.0% by mass). Mw of the copolymer (A-1) was 14,200. Reprecipitation purification was performed by dropping the copolymer (A-1) into hexane, and the reaction rate of glycidyl methacrylate was calculated by ¹ H-NMR analysis for the reprecipitated resin solids. Integration between the peak derived from the methacrylic group of glycidyl methacrylate at around 6.1 ppm and 5.6 ppm and the proton of the aromatic ring around 6.8 ppm to 7.4 ppm derived from the structural unit of benzyl methacrylate in the copolymer From the comparison of the ratio, the reaction rate between glycidyl methacrylate and the carboxy group in the copolymer was calculated. As a result, it was confirmed that 96 mol% of the reacted glycidyl methacrylate reacted with the carboxy group in the copolymer.

[Synthesis Example 2] (A-2) Synthesis of alkali-soluble resin having epoxy group in side chain 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) in a flask equipped with a condenser and a stirrer And 220 parts by mass of diethylene glycol ethyl methyl ether were charged. Subsequently, 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, 30 parts by mass of styrene, 30 parts by mass of N-cyclohexylmaleimide, and 7 parts by mass of α-methylstyrene dimer were charged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2).

<Synthesis of binder resin>
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 235 parts by mass of propylene glycol monomethyl ether acetate, followed by 20 parts by mass of methacrylic acid and 12 parts by mass of N-phenylmaleimide. Then, 14 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate, and 5 parts by mass of α-methylstyrene dimer (chain transfer agent) were charged and substituted with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring, and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby a binder resin ( A polymer solution containing c-1) was obtained.

<Preparation of pigment dispersion>
[C] As a colorant (black pigment), a compound represented by the above formula (4) (R ^{1 to} R ¹⁰ are hydrogen atoms) and a compound represented by the above formula (5) (R ^{11 to} R). ²⁰ is a hydrogen atom) 15 parts by mass of a mixture with an acrylic copolymer as a dispersant (5 parts by mass of “BYK-LPN21116” manufactured by BYK (BYK)), and a binder resin (c-1) as a polymer 5 parts by mass and 75 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed by a bead mill to prepare a pigment dispersion (C-1).

[Examples 1 to 6 and Comparative Examples 1 to 4] <Preparation of radiation-sensitive colored composition>
A solution (polymer solution) containing [A] polymer of the type and blending amount (parts by mass) shown in Table 1, [B] photopolymerization initiator, [C] pigment dispersion containing colorant, [D] thiol 0.2 parts by mass of a system compound, [E] polyfunctional acrylate, and silicone surfactant (“SH8400 FLUID” manufactured by Toray Dow Corning Silicone) were mixed. Propylene glycol monomethyl ether acetate (PGMEA) was further added to this mixture so that the solid content concentration was 25% by mass to prepare a radiation-sensitive colored composition.
“-” In Table 1 indicates that it is not blended.

In addition, each symbol in Table 1 is as follows.
[A] Polymer (polymer solution)
A-1: Alkali-soluble resin having a methacryloyl group in the side chain obtained in Synthesis Example 1 (solid content concentration: 40% by mass)
A-2: Alkali-soluble resin having an epoxy group in the side chain obtained in Synthesis Example 2 (solid content concentration: 40% by mass)
A-3: Cardo resin having an acryloyl group and a carboxy group (“Ogsol CR-1030” manufactured by Osaka Gas Chemical Co., Ltd.) (solid content concentration: 50% by mass)
A-4: Acid-modified epoxy acrylate resin (“ZCR-1797H” manufactured by Nippon Kayaku Co., Ltd.) (solid content concentration: 65 mass%)
[B] Photopolymerization initiator b-1: 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (“Irgacure (registered trademark) OXE01” manufactured by BASF)
b-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (“Irgacure (registered trademark)” manufactured by BASF OXE02 ")
B-3: Compound represented by the following formula

[C] Colorant C-1: Pigment dispersion [D] Thiol-based compound D-1: Pentaerythritol tetrakis (3-mercaptopropionate)
D-2: Pentaerythritol tetrakis (3-mercaptobutyrate) (“Karenz MTPE1” manufactured by Showa Denko KK)
[E] Multifunctional acrylate E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)

<Characteristic evaluation>
The following characteristic evaluation was performed using the radiation sensitive coloring composition prepared in Examples 1-6 and Comparative Examples 1-4.

<Formation of cured film>
After applying the radiation sensitive coloring composition prepared in Examples 1 to 6 and Comparative Examples 1 to 4 on a glass substrate (“Corning (registered trademark) 7059” manufactured by Corning) using a spinner, And prebaked at 90 ° C. for 2 minutes to form a coating film. After cooling these substrates to room temperature, each coating film was irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 J / m ² without using a photomask using a high-pressure mercury lamp. (Hereinafter also referred to as “exposure”). Then, shower development was performed for 60 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate is washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes, whereby a cured film for evaluation having a post-baked film thickness of 3.0 μm is obtained. Formed.

<HPLC evaluation>
The cured film was shaved into powder, mixed with liquid crystal (“MLC6608” manufactured by Merck), and then heated at 120 ° C. for 60 minutes to elute impurities in the cured film into the liquid crystal. Thereafter, the cured film in the liquid crystal was removed by filtration using a PTFE filter to obtain a liquid crystal extract. The liquid crystal extract was diluted 100 times with THF, and analysis was performed using “LC / MS6130” (column: Capcelpak C18, developing solvent: methanol) manufactured by Agilent Technologies. The liquid crystal extract and the liquid crystal chart were compared, and when there was a peak only in the liquid crystal extract, it was determined that impurity elution was present.

<Voltage holding ratio VHR>
On a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, an alignment film forming composition (manufactured by JSR Corporation, “ AL65008 ") was applied using a spinner. Thereafter, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes, and further post-baked in a clean oven at 200 ° C. for 30 minutes to form a coating film having a thickness of 100 nm. Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the alignment film, a liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate in which an ITO electrode is deposited in a predetermined shape on the surface. The remaining four sides were bonded using a sealing agent mixed with 0.8 mm glass beads, and after injecting the liquid crystal extract, the liquid crystal inlet was sealed to prepare a liquid crystal cell. This liquid crystal cell was put in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (“VHR-1A type” manufactured by Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value calculated from the following equation. The lower the voltage holding ratio, the more the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, which means that the liquid crystal cannot be sufficiently aligned. There is a high risk of causing
Voltage holding ratio (%) = (potential difference of liquid crystal cell after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds) × 100

  As shown in Table 1, in the cured films obtained from the radiation-sensitive colored compositions of Examples 1 to 6, there was no HPLC peak, and elution into the liquid crystal was not confirmed. Moreover, it was confirmed that the liquid crystal display element obtained using the radiation sensitive coloring composition of Examples 1-6 has a high voltage retention.

The radiation-sensitive colored composition of the present invention can be suitably used as a material for forming a colored pattern that becomes a spacer or the like of a liquid crystal display element.

Claims (8)

Polymer,
A photopolymerization initiator having two or more sites represented by the following formula (1) in one molecule, and a colorant having a lactam structure, this isomer ring structure or a combination thereof,
Radiation-sensitive colored composition for forming a spacer of a liquid crystal display element (however, a base having an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group and a halosulfonyl group) Excluding those containing a reactive colorant and an intermolecular hydrogen abstraction type photo radical initiator or biimidazole compound).

(In the formula (1), R ^X represents a monovalent organic group.) The radiation-sensitive colored composition according to claim 1, wherein the colorant has at least one of a site represented by the following formula (2) and a site represented by the following formula (3).

The radiation-sensitive colored composition according to claim 2, wherein the colorant is at least one of a colorant represented by the following formula (4) and a colorant represented by the following formula (5).

(In Formula (4) and Formula (5), R < ¹ >, R < ⁶ >, R < ¹¹ > and R <^16> are respectively independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or C1-C6. Of the fluorinated alkyl group.
R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ¹⁵ and R ^{17 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, or R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH _2. , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , OCOR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²¹ , NR ²¹ COR _{^{22, N = CH 2, N}} = CHR 21, N = CR 21 R 22, SH, SR 21, SOR 21, SO 2 R 21, SO 3 R 21, SO 3 H, SO 3 ^over, _SO 2 _NH 2, It is a group represented by SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² . The groups bonded to adjacent carbon atoms among R ^{2 to} R ⁵ , R ^{7 to} R ¹⁰ , R ^{12 to} R ^15, and R ^{17 to} R ²⁰ are each directly or —O—, —S—, —NH. They may be bonded via — or —NR ²¹ —, and may form a ring structure together with the carbon atom to which they are bonded.
R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 12 carbon atoms, or An alkynyl group having 2 to 12 carbon atoms, or a group in which —O—, —NH—, —NR ²³ — or —S— is interposed between carbon-carbon bonds of these groups, and this alkyl group, cycloalkyl group , An alkenyl group, a cycloalkenyl group, and an alkynyl group have a part or all of a halogen atom, COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, ═O, OH, OR ²³ , OCOR ²³ , OCONH ₂ , OCONHR ²³ , OCONR ²³ R ²⁴ , ═NR ²³ , NH ₂ , NHR ²³ , NR ²³ R ²⁴ , NHCOR ²⁴ , NR ²³ COR ²⁴ , N = CH ₂ , N = CHR ²³ , N = CR ²³ R ²⁴ , SH, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H , SO _{3 ^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 group represented by ^{R 24,} aralkyl group having 7 to 12 carbon atoms, 6 to a heteroaryl group or a carbon number of 1 to 11 carbon atoms It may be substituted with 12 aryl groups. Part or all of the hydrogen atoms of the aralkyl group, heteroaryl group, and aryl group are a halogen atom, or COOH, COOR ²³ , COO ⁻ , CONH ₂ , CONHR ²³ , CONR ²³ R ²⁴ , CN, OH, OR ^{23. _{, OCOR 23, OCONH 2, OCONHR}} 23, OCONR 23 R 24, NO 2, NH 2, NHR 23, NR 23 R 24, NHCOR 24, NR 23 COR 24, N = CH 2, N = CHR 23, N = CR ²³ R ^{24, SH,} represented by _{^{SR 23, SOR 23, SO 2}} R 23, SO 3 R 23, SO 3 H, SO 3 _{^over, SO 2 NH 2, SO 2} NHR 23 or _SO 2 ^NR 23 ^{R 24} It may be substituted with a group.
R ²³ and R ²⁴ are each independently an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group, and R ²³ and R ²⁴ may be directly or —O—, —S—, —NH—. Or it couple | bonds through -NR < ²⁵ >-and you may form the ring structure with the atom which these couple | bond.
R ²⁵ is a monovalent organic group. )   The radiation-sensitive colored composition according to claim 1, 2 or 3, wherein the polymer has a cyclic ether group, a (meth) acryloyl group, a vinyl group or a combination thereof. The radiation-sensitive colored composition according to any one of claims 1 to 4, wherein the photopolymerization initiator is a photopolymerization initiator represented by the following formula (6).

(In formula (6), two R ^{1A s} are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a 2-furyl group. , 2-furfuryl group, 2-thienyl group, 2-thenyl group, phenyl group or naphthyl group, part or all of the hydrogen atoms of the phenyl group or naphthyl group are alkyl groups having 1 to 6 carbon atoms, carbon It may be substituted with an alkoxy group of 1 to 6 or a halogen atom.
R ^2A and R ^3A are each independently an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
R ^4A is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a 2-furyl group, a 2-furfuryl group, a 2-thienyl group, or a 2-thenyl group.
R ^5A is a sulfo group or a group represented by SO ₂ R ^6A , P (R ^7A ) ₂ , PO (R ^8A ) ₂ or Si (R ^9A ) ₃ .
R ^6A is a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms are a carboxy group, A methoxycarbonyl group, an ethoxycarbonyl group, an acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group, or an acyl group having 1 to 20 carbon atoms may be substituted, or a part of hydrogen atoms of the phenyl group or naphthyl group or All may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
R ^7A , R ^8A and R ^9A are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or naphthyl group have a carbon number It may be substituted with a 1-6 alkyl group, a C1-C6 alkoxy group or a halogen atom. ) Using the radiation-sensitive colored composition according to any one of claims 1 to 5 to form a coating film on a substrate;
Irradiating a part of the coating film with radiation,
A method of forming a spacer , comprising: developing a coating film irradiated with the radiation; and heating the developed coating film. The spacer formed from the radiation sensitive coloring composition of any one of Claims 1-5. A liquid crystal display device comprising the spacer according to claim 7.