KR20160098033A - Radiation-sensitive colored composition, colored pattern and process for forming the same, and liquid crystal display device - Google Patents

Abstract

The present invention provides a radiation-sensitive colored composition capable of forming a colored pattern which reduces contamination of a liquid crystal layer due to a coloring agent; a colored pattern formed in the radiation-sensitive colored composition; a process for forming the same; and a liquid crystal display device comprising the colored pattern. According to the present invention, the radiation-sensitive colored composition comprises: a polymer; a photopolymerizable initiator having at least two moieties represented by formula (1) per molecule; and a coloring agent having a lactam structure, two isomeric ring structures or a combination thereof. The polymer preferably includes groups such as a cyclic ether group and a (meth)acryloyl group. The process for forming a colored pattern uses the radiation-sensitive colored composition in the processes for forming a film on a substrate; irradiating radioactive rays on a part of the film; developing the film irradiated with the radioactive rays; and heating the developed film. In the formula (1), R^X represents a monovalent organic group.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive coloring composition, a coloring pattern, a method of forming the same, and a liquid crystal display device,

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

Photolithography is used to form a spacer for maintaining a gap (cell gap) between substrates in a liquid crystal display element. In this method, a radiation sensitive composition is coated on a substrate, exposed to radiation such as ultraviolet rays through a predetermined mask and developed, and a dot or stripe pattern is formed as a spacer (Japanese Patent Application Laid-Open 2001-302712).

Recently, a so-called black column spacer has been proposed in which the spacers are made light-shielding by a coloring agent such as carbon black (see Japanese Patent Laid-Open Publication No. 2011-170075). However, when a coloring pattern such as a black column spacer is employed, contamination of the liquid crystal layer tends to occur due to leaching of the coloring agent into the liquid crystal layer in the colored pattern. Such contamination of the liquid crystal layer causes a decrease in the voltage holding ratio of the liquid crystal display element.

Japanese Patent Application Laid-Open No. 2001-302712 Japanese Laid-Open Patent Publication No. 2011-170075

The object of the present invention is to provide a radiation-sensitive coloring composition capable of forming a coloring pattern in which contamination of a liquid crystal layer by a coloring agent is reduced, a coloring pattern formed of the radiation- A method of forming the same, and a liquid crystal display element having the colored pattern.

The invention made to solve the above problems is a photopolymerization initiator (hereinafter, also referred to as a "photopolymerization initiator") having at least two sites in the molecule represented by the following formula (1) ), And a colorant having a lactam structure, an isomeric ring structure, or a combination thereof (hereinafter, also referred to as "[C] colorant"))

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

It is preferable that the coloring agent has at least one of a site represented by the following formula (2) and a site represented by the following formula (3).

It is preferable that the coloring agent is at least one of a coloring agent represented by the following formula (4) and a coloring agent represented by the following formula (5)

(Wherein 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 fluoride group having 1 to 6 carbon atoms ;

R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ each independently represent 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, SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ; Groups bonded to adjacent carbon atoms of R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ may be bonded to each other directly or by -O-, -S-, -NH- or - NR ²¹ - and may form a cyclic structure together with the carbon atom to which they are bonded;

R ²¹ and R ²² each independently represent 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 the carbon-carbon bonds of these groups, and the hydrogen having the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group and alkynyl group some or all of the atoms, 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 ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ , an aralkyl group having 7 to 12 carbon atoms, 11 heteroaryl group or an aryl group having 6 to 12 carbon atoms, It may be good; Some or all of the aralkyl group, a heteroaryl group, and hydrogen atom having an aryl group, the 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, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ Good;

R ²³ and R ²⁴ are, each independently, an alkyl group, a benzyl group or a phenyl group having a carbon number of 1~6, R ²³ and R ²⁴ are, directly or -O-, -S-, -NH- or -NR ²⁵ - the And may form a cyclic structure together with the atoms to which they are bonded;

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.

It is preferable that the photopolymerization initiator is a photopolymerization initiator represented by the following formula (6)

(In the formula (6), two R &^lt; ^1A > independently represent 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, , A 2-thienyl group, a 2-thenyl group, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, It may be good;

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 represents 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-thienyl 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 represents a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and a part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms may be substituted with a carboxyl group, a methoxycarbonyl group, An acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group or an acyl group having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms of the phenyl group or the 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;

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 the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group of 1 to 6 carbon atoms or a halogen atom).

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

Another invention made to solve the above problems is to provide a process for producing a radiation sensitive film, which comprises a step of forming a coating film on a substrate using the radiation sensitive coloring composition, a step of irradiating a part of the coating film with radiation, And a step of heating the developed coating film.

Another invention made to solve the above problems is a liquid crystal display element comprising a coloring pattern formed of the radiation-sensitive coloring composition and the coloring pattern.

The radiation sensitive coloring 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 coloring pattern and the liquid crystal display element of the present invention, the contamination of the liquid crystal layer by the coloring agent is reduced, and the coloring pattern forming method of the present invention can form such a coloring pattern.

(Mode for carrying out the invention)

<Radiation-sensitive coloring composition>

The radiation-sensitive coloring composition contains the [A] polymer, the [B] photopolymerization initiator and the [C] colorant.

<[A] Polymer>

As the polymer [A], conventionally known ones used in the radiation-sensitive composition may be used. The polymer [A] 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 with respect to an alkali developer.

(Copolymer (?))

As the resin having a carboxy group, an unsaturated compound (hereinafter referred to as &quot; compound (a1) &quot;) other than (a1) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a combination thereof (a2) &quot;) is preferable.

As specific examples of the compound (a1)

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid And the like;

Dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid;

And the acid anhydrides of the above-mentioned dicarboxylic acids.

In the copolymer (?), The compound (a1) may be used alone or in combination of two or more. In the copolymer (), 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 further preferably 10% by mass. On the other hand, the upper limit is preferably 60% by mass, more preferably 50% by mass, still more preferably 40% by mass. By setting the content ratio of the structural unit derived from the compound (a1) within this range, a radiation sensitive coloring composition in which various properties such as radiation sensitivity and developability are balanced to a higher level can be obtained.

As specific examples of the compound (a2)

Acrylic acid alkyl esters such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate and t-butyl acrylate;

Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, ester;

2-methylcyclohexyl acrylate, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl , Acrylic acid alicyclic ester such as isobornyl acrylate;

2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxy) ethyl methacrylate, isobornyl methacrylate and the like;

Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;

Hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate;

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;

An oxygen-containing complex five-membered ring or an acrylic acid ester having an oxygen-containing complex 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, or 2-methyltetrahydropyran-2-yl acrylate;

An oxygen-containing complex 5-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran- Methacrylic acid esters;

Vinyl aromatic compounds such as styrene,? -Methylstyrene, and p-methoxystyrene;

Conjugated diene-based compounds such as 1,3-butadiene and isoprene;

(Meth) acrylic acid ester having a vinyl group or a cyclic ether group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and allyl (meth) acrylate;

In addition, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and the like can be mentioned.

In the copolymer (?), The compound (a2) may be used alone or in combination of two or more. In the copolymer (), 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, still more preferably 30% by mass. On the other hand, the upper limit is preferably 70% by mass, more preferably 60% by mass, still more preferably 50% by mass. When the content ratio of the structural unit of the compound (a2) is within this range, the control of the molecular weight of the copolymer is facilitated, and a radiation sensitive coloring composition balanced in development and radiation sensitivity is obtained.

The copolymer (?) Can be produced by a known method. (Weight average molecular weight), Mn (number-average molecular weight), and number average molecular weight (number average molecular weight), by the method disclosed in Japanese Unexamined Patent Application Publication No. 2003-222717, Japanese Unexamined Patent Application Publication No. 2006-259680, Average molecular weight), Mw / Mn, and the like.

As the polymer (A), a (meth) acrylic acid ester having a cyclic ether group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexyl (meth) acrylate is reacted with the carboxy group of the copolymer , And (meth) acryloyl groups may be used. Such copolymers include, for example, those described in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-09-325494, 11-140144, and JP-A-2008-181095.

(Carded resin)

As the polymer [A], it is also preferable to use a cadmium resin. Examples of such a polymer [A] include a polymer obtained by adding a compound represented by the following formula (8) to a polymer obtained by reacting a compound having a fluorene skeleton represented by the following formula (7) with a tetrabasic acid dianhydride .

　

In the formula (7), the ring Z ¹ and the 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 each independently represent 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; In the case where the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings, p ¹ and p ² are each independently an integer of 1 to 3, and when the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings, the ring Z ¹ And the sum of p &lt; ² &gt; included in the ring Z &lt; ² &gt;

In the 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 (9-2). * Represents the binding site.

In the 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 the hydrocarbon ring is a monocyclic or condensed polycyclic hydrocarbon. Examples thereof include monocyclic hydrocarbons such as benzene, condensed bicyclic hydrocarbons (e.g., condensed bicyclic hydrocarbons having 8 to 20 carbon atoms such as indene and naphthalene , Condensed bicyclic hydrocarbons having preferably 10 to 16 carbon atoms), and condensed polycyclic hydrocarbons such as condensed tricyclic hydrocarbons (e.g., anthracene, phenanthrene, etc.). Particularly preferred hydrocarbons for applications requiring high refractive index and heat resistance include condensed polycyclic aromatic hydrocarbons, and naphthalene is particularly preferred. Furthermore, benzene is particularly preferred for applications requiring high solubility, compatibility and low solution viscosity.

Examples of the alkyl group represented by R ^1a and R ^1b in the formula (7) include 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 and a t-butyl group. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is more preferable. As 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 above 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 . 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 and an adamantyl group, Cycloalkyl group is preferable, and a cycloalkyl group having 5 to 8 carbon atoms is more preferable. 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 an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group and a benzooxy group. Examples of the acyl group represented by R ^2a and R ^2b in the above formula (7) include an acyl group having 2 to 13 carbon atoms such as a 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 an alkoxycarbonyl group having 2 to 13 carbon atoms such as a methoxycarbonyl group, ethoxycarbonyl group and benzooxycarbonyl group. Examples of the halogen atom represented by R ^2a and R ^2b in the above formula (7) include a fluorine atom and a chlorine atom.

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

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

The upper limit of p1 and p2 in the 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, more preferably 4. This lower limit can be set to 2. P1 and p2 are preferably 2 and 3, particularly in applications where the crosslinking density of the cured product is required.

The plurality of hydroxyl group-containing groups constituting the same phenol skeleton may be the same or different. For example, a plurality of hydroxyl group-containing groups may be composed of (i) a hydroxyl group having n1 = 0 (n2 = 0) (except when p1 and p2 are 2) ) may be composed of a hydroxyl group of n1 = 0 (n2 = 0) and a hydroxy (poly) alkoxy group of n1 ≠ 0 (n2 ≠ 0) (such as 2-hydroxyethoxy group) (Poly) alkoxy groups of the same hydroxy (poly) alkoxy group of which n1 is not 0 (n2 ≠ 0) and (iv) different hydroxy (poly) alkoxy groups Hydroxyethoxy group and a 2- (2-hydroxyethoxy) ethoxy group].

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

Examples of the 9,9-bis (hydroxyalkoxynaphthyl) fluorenes include 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9- Fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, And 9,9-bis (hydroxy C2-4 alkoxynaphthyl) fluorene such as [5- (2-hydroxypropoxy) -1-naphthyl] fluorene.

Examples of the 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes include 9,9-bis {6- [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl} Fluorene, 9,9-bis {5- [2- (2-hydroxy-2-hydroxyphenyl) Ethoxy] -1-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxypropoxy) propoxy] And bis (hydroxy dialkoxynaphthyl) fluorenes.

Examples of the tetrabasic acid dianhydride include butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic acid Biphenyltetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, cycloheptanetetracarboxylic acid dianhydride, cycloheptanetetracarboxylic acid dianhydride, cycloheptanetetracarboxylic acid dianhydride, , 2,5- dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran- -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,4 '- (hexafluorois Propylidene) diphthalic acid anhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid 2-anhydride and the like. Among these, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, benzophenonetetracarboxylic acid 2 Anhydrides and biphenyltetracarboxylic dianhydrides are preferred.

The ratio of the tetrabasic acid dianhydride to 1 mol of the compound having a fluorene skeleton in the reaction of the compound having the fluorene skeleton with the tetrabasic acid dianhydride is, for example, 0.5 mol or more and 1.5 mol or less. Outside this range, a sufficient molecular weight may not be obtained.

In the reaction of the compound having a fluorene skeleton with the tetrabasic acid 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, 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 and tetramethylammonium hydroxide, tributylphosphine , Triphenylphosphine, and the like. 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 based on 100 parts by mass of the total amount of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. When the amount of the catalyst is more than 2.0 parts by mass, the electrical properties and storage stability may be adversely affected.

In the course of the reaction, a solvent may be used for the purpose of dissolving the reaction raw materials, reducing viscosity, and the like. The solvent is not particularly limited so long as it does not inhibit the reaction. Examples of the solvent include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Propylene glycol ethers such as dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether and dipropylene glycol diethyl ether; glycol ether esters such as ethylene glycol monobutyl ether acetate and diethylene glycol monobutyl ether acetate; , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate, acetone, Methyl ethyl ketone, cyclohexanone and the like, acetic acid esters such as ethyl acetate and butyl acetate, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and mixtures thereof .

The amount of the solvent to be used is not particularly limited, but is preferably in the range of 25 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the total amount of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. When the amount is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, if it exceeds 150 parts by mass, the concentration of the reactant may be too low to lower the reaction rate.

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

In the reaction of the polymer with the carbonic acid-reactive (meth) acrylate compound, a catalyst may be used for promoting the reaction. Examples of the catalyst include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7- undecene, Quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and tetramethylammonium hydroxide; amines such as quaternary ammonium compounds such as tributylphosphine, Triphenylphosphine, and the like, and mixtures thereof.

When the carbonic acid reactive (meth) acrylate is reacted, it is preferable to add a polymerization inhibitor. The polymerization inhibitor is not particularly limited as long as it inhibits the reaction of the unsaturated bond. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, Aniline, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy- 2,6,6-tetramethylpiperidine-1-oxyl, and the like.

(Other configurations, etc.)

The polymer [A] is not limited to the above-mentioned copolymer (?) Or cadoline resin.

The polymer [A] is preferably a polymer having a polymerizable group such as cyclic ether group, (meth) acryloyl group, vinyl group, or a combination thereof. Examples of the cyclic ether group include an oxiranyl group and an oxetanyl group. By using such a polymer having a polymerizable group, elution of [C] coloring agent in a coloring pattern obtained from the radiation sensitive coloring composition can be reduced. Examples of the polymer (A) include (1) a copolymer into which a (meth) acryloyl group is introduced by using a carbonic acid-reactive (meth) acrylate or the like with respect to the copolymer ) Copolymer obtained by using the above-mentioned cyclic ether group or vinyl group-containing (meth) acrylic acid ester as the compound (a2) in the copolymer (?), And other copolymers obtained by using a polymerizable group such as an epoxy acrylate resin Epoxy resins and the like. As the epoxy acrylate resin, an acid-modified alkali-soluble resin is suitably used.

The lower limit of the content of the structural unit having a polymerizable group in the [A] polymer is preferably 5% by mass, more preferably 10% by mass. On the other hand, the upper limit is preferably 50% by mass, more preferably 40% by mass. By setting the content ratio of the structural unit having a polymerizable group within this range, it is possible to effectively dissolve the coloring agent while sufficiently providing developability and the like.

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

The [A] polymers may be used alone or in combination of two or more.

&Lt; [B] Photopolymerization initiator &gt;

[B] The photopolymerization initiator has at least two sites in the molecule represented by the above formula (1). [B] Since the photopolymerization initiator [B] has a plurality of the above sites, it is possible to form a coloring pattern having excellent radiation sensitivity and inhibiting elution of the [C] coloring agent.

The monovalent organic group represented by R ^X in the formula (1) is not particularly limited as long as it is a group containing at least one carbon atom, and examples thereof include a hydrocarbon group such as an alkyl group and a cycloalkyl group, a haloalkyl group, A thienyl group, a 2-thienyl group, a phenyl group, a naphthyl group, and a group formed by combining these groups. Some or all of the hydrogen atoms of the phenyl group or the 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.

As the alkyl group represented by R ^X , those exemplified as R ^1a and the like can be mentioned, and an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.

As the cycloalkyl group represented by R ^X , those exemplified as the cycloalkyl group represented by R ^2a and the like can be mentioned, and a cycloalkyl group having 4 to 20 carbon atoms is preferable.

The haloalkyl group represented by R ^X is a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom and includes, for example, 1 to 6 carbon atoms such as a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, Of haloalkyl groups.

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

In formula (6), the plurality of R &^lt; ^1A &^gt; each independently represents 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, A thienyl group, a 2-thienyl group, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, good.

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 represents 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-thienyl group.

R ^5A represents 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 represents a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and a part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms may be substituted with a carboxyl group, a methoxycarbonyl group, An acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group or an acyl group having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms of the phenyl group or the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group of 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 the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group of 1 to 6 carbon atoms or a halogen atom.

Specific examples of each group represented by R ^1A include those exemplified as groups 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 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 cycloalkyl group having 3 to 10 carbon atoms represented by R ^2A and R ^3A include those exemplified as groups represented by R ^1a and R ^2a . As R ^2A and R ^3A, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

Examples of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms represented by R ^4A include those exemplified as groups represented by R ^1a and R ^2a . 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 still more preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the alkyl group having 2 to 12 carbon atoms represented by R ^6A include those exemplified as groups represented by R ^1a . Examples of the acyloxy group having 1 to 6 carbon atoms as a substituent include an acetoxy group and a propionyloxy group. Examples of the acyl group having 1 to 20 carbon atoms as the substituent include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group and a hexanoyl group.

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

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

R ^5A is a group represented by SO ₂ R ^6A , PO (R ^8A ) ₂ or Si (R ^9A ) ₃ , and R ^5A is a group represented by R ¹ , R ^{2 A} , R ^{3 A} and R ^4A , , wherein R ^6A is a part or all of the hydrogen atoms and the alkyl group having a carbon number of 2 to 6 substituted with an acetoxy group, wherein R ^8A is a phenyl group, it is the R ^9A is preferred that the alkyl group having 1 to 6 carbon atoms. By such a structure, it is possible to improve the solubility and the like.

The compound represented by the formula (6) can be obtained by the production method described in, for example, Japanese Patent Laid-Open Publication No. 2011-178776.

The content of the [B] photopolymerization initiator in the radiation-sensitive coloring composition is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more per 100 parts by mass of the polymer (solid content) desirable. On the other hand, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.

&Lt; [B '] Photopolymerization initiator &gt;

The radiation-sensitive coloring composition may contain a photopolymerization initiator [B] together with [B] a photopolymerization initiator. [B '] Examples of the photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, , an? -diketone compound, a polynuclear quinone compound, a diazo compound, and an imidosulfonate compound.

The total content of the [B] photopolymerization initiator and the [B '] photopolymerization initiator in the radiation sensitive coloring composition is not particularly limited, but the lower limit is, for example, 5 parts by mass per 100 parts by mass of the [A] More preferably 10 parts by mass. On the other hand, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.

&Lt; [C] Colorant &gt;

[C] Colorant is a colorant having a lactam structure, an isomeric 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 isomeric 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.

The [C] colorant is not particularly limited as long as it has a lactam structure, an isomeric ring structure, or a combination thereof. It is preferable that the colorant has at least one of the moiety represented by the formula (2) and the moiety represented by the formula (3) desirable. A substituent may be bonded to the benzene ring in the formulas (2) and (3). Examples of such a coloring agent include a bis-oxodihydroindolylene-benzodipuranone colorant having a structure in which two of the above-mentioned moieties are substituted in the benzodifuranone skeleton, isomers thereof, or tautomers thereof.

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

In the formulas (4) and (5), R ¹ , R ⁶ , R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, .

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 fluorinated alkyl group having 1 to 6 carbon atoms Or a group in which all or part of them is substituted with a fluorine atom.

R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ each independently represent 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, SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² . Groups bonded to adjacent carbon atoms of R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ may be bonded to each other directly or by -O-, -S-, -NH- or - NR ²¹ - may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.

R ²¹ and R ²² each independently represent 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 the carbon-carbon bonds of these groups, and the hydrogen having the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group and alkynyl group some or all of the atoms, 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 ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ , an aralkyl group having 7 to 12 carbon atoms, 11 heteroaryl group or an aryl group having 6 to 12 carbon atoms, It is also good. Some or all of the aralkyl group, a heteroaryl group, and hydrogen atom having an aryl group, the 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, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ good.

= O and = NR &lt; ²³ &gt; represent that two hydrogen atoms bonded to the carbon atom of 1 are substituted with O or NR &lt; ^{23 &} gt ;.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ²¹ and R ²² include those exemplified as the alkyl group represented by R ^1a . Examples of the cycloalkyl group having 3 to 12 carbon atoms include those exemplified as cycloalkyl groups represented by R ^2a . Examples of the alkenyl group having 2 to 12 carbon atoms include an ethynyl group (vinyl group) and a propenyl group (allyl group). Examples of the cycloalkenyl group having 4 to 12 carbon atoms include a cyclopentenyl group, a cyclohexenyl group and a cyclooctenyl group. Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group and a propynyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group and a phenethyl group. Examples of the heteroaryl group having 1 to 11 carbon atoms include groups having an aromatic ring having a reduced number of 5 to 12 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, a benzyl group or a phenyl group having a carbon number of 1~6, R ²³ and R ²⁴ are, directly or -O-, -S-, -NH- or -NR ²⁵ - the And may form a ring structure together with the atoms to which they are bonded.

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 .

R ²⁵ is a monovalent organic group. As the monovalent organic group, those exemplified as a monovalent organic group represented by R ^X can be mentioned.

When the coloring agent represented by the formula (4) and the coloring agent represented by the formula (5) are anion, they exist as an ionic compound together with the 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 organometallic ions.

As the R ¹ , R ² , R ⁴ to R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ to R ¹⁷ , R ¹⁹ and R ²⁰ , a hydrogen atom, a fluorine atom and a chlorine atom are preferable, More preferable. R ^3, R ^8, R ^13, and as the R ^18, a hydrogen atom, NO _2, OCH _3, OC ₂ H _5, a bromine atom, a 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 group, β-naphthyl group and SO ₃ ^- . 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 coloring agent represented by the formula (4) and the coloring agent represented by the formula (5) can be produced, for example, by the method described in WO 2000/24736.

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

The content of the [C] colorant is not particularly limited, but is preferably 5 parts by mass, more preferably 10 parts by mass, and further preferably 20 parts by mass as a lower limit to 100 parts by mass of the solid content in the radiation sensitive coloring composition. On the other hand, the upper limit is preferably 60 parts by mass, more preferably 50 parts by mass, still more preferably 40 parts by mass. By setting the content of the [C] colorant to such a range, a sufficiently colored pattern can be obtained while inhibiting dissolution of the colorant.

<[C '] Other colorants>

In the radiation-sensitive coloring composition, other colorants other than the [C] colorant may be used together with the purpose of adjusting the color tone and the like. [C '] Other coloring agents include known pigments and dyes.

As the pigment, any of organic pigments and inorganic pigments may be used. As the organic pigment, for example, a compound classified by pigment in the color index (C.I., published by The Society of Dyers and Colourists) may be mentioned. Specifically, a color index (C.I.) name as described below is attached.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211;

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

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

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, spinach (red iron oxide (III)), cadmium red, Green, umber, titanium black, synthetic iron black, and carbon black.

The dyes can be appropriately selected from among various kinds of oil-soluble dyes, direct dyes, acid dyes, metal complex dyes and the like, for example, those having the following color index (C.I.) names.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent Yellow 179;

C.I. Solvent Red 45, C.I. Solvent Red 49;

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67;

C.I. Acid Yellow 17, C.I. Acid Yellow 29, C.I. Acid Yellow 40, C.I. Acid Yellow 76;

C.I. Acid Red 91, C.I. Acid Red 92, C.I. Acid Red 97, C.I. Acid Red 114, C.I. Acid Red 138, C.I. Acid Red 151;

C.I. Acid Orange 51, C.I. Acid Orange 63;

C.I. Acid Blue 80, C.I. Acid Blue 83, C.I. Acid Blue 90;

C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, C.I. Acid Green 27.

[C '] Other coloring agents may be used alone or in combination of two or more.

The total content of the [C] coloring agent and the [C '] other coloring agent in the radiation sensitive coloring composition is preferably 5 parts by mass, more preferably 10 parts by mass, and more preferably 20 parts by mass as the lower limit to 100 parts by mass of the total solid content More preferred is the addition. On the other hand, the upper limit is preferably 60 parts by mass, more preferably 50 parts by mass, still more preferably 40 parts by mass. By setting the total content of the coloring agent to this range, it is possible to obtain a sufficiently colored pattern while suppressing the elution of the coloring agent.

&Lt; Other optional components &gt;

The radiation-sensitive coloring composition may contain a thiol compound, a polyfunctional acrylate, a compound having a cyclic ether group, a surfactant, an adhesion aid, a dispersant, a dispersion aid, a solvent, etc. May also contain other optional components. The other optional components may be used singly or in combination of two or more. Each component will be described in detail below.

<Thiol compound>

The 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. Such a compound includes, for example, a compound represented by the following formula (10).

In the 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 of these groups may be substituted with an alkyl group. Y ¹ is a single bond, -CO- or -O-CO- *. However, a combined hand with an asterisk (*) is combined with R ³³ . n is an integer of 2 to 10; A ¹ is an n-valent hydrocarbon group of 2 to 70 carbon atoms which may have one or more ether bonds, or when n is 3, a group represented by the following formula (11).

In the formula (11), R ³⁴ to R ³⁶ each independently represent a methylene group or an alkylene group having 2 to 6 carbon atoms. "*" Is a combined hand.

Typical examples of the compound represented by the formula (10) include esters of mercaptocarboxylic acid and 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, trimethylol propane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol and pentaerythritol.

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

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

　

In the formula (12), R ⁴¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms. R ⁴² is a methylene group or an alkylene group having 2 to 6 carbon atoms. k is an integer of 1 to 20;

In the above formula (13), R ⁴³ to R ⁴⁶ each independently represent a hydrogen atom, a hydroxyl group or a group represented by the following formula (14). Provided that 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 may be used alone or in combination of two or more. The lower limit of the content of the thiol compound in the radiation-sensitive coloring composition is preferably 0.5 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 20 parts by mass, more preferably 15 parts by mass. If the content of the thiol compound is less than the above lower limit, the effect of improving the curability is not sufficiently obtained, and if it exceeds the upper limit, the pattern shape may be damaged.

<Polyfunctional acrylate>

It is possible to increase the hardness of the obtained pattern by containing the polyfunctional acrylate in the radiation sensitive coloring composition. Examples of 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 Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol di (meth) acrylate, (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 Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxyphenyl (meth) acrylate, (Meth) acryloyloxypropyl (meth) acrylate, ethyleneglycol diglycidylether di (meth) acrylate, diethyleneglycol diglycidylether di (meth) acrylate, phthalic acid diglyme (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene A reaction product of a diisocyanate and 2-hydroxyethyl (meth) acrylate, a condensation product of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) Of It may include a functional monomer, or an acrylic conformal tree or the like. These polyfunctional acrylates may be used alone or in combination of two or more.

The lower limit of the content of the polyfunctional acrylate is preferably 10 parts by mass, more preferably 30 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 150 parts by mass. By setting the content of the polyfunctional acrylate within this range, it is possible to further increase the hardness of the obtained pattern and to increase the radiation sensitivity of the radiation sensitive coloring composition.

&Lt; Compound having cyclic ether group &gt;

The compound having a cyclic ether group has a cyclic ether group and is a compound other than the [A] polymer (e.g., a low molecular weight compound having a molecular weight of 1,000 or less). The present radiation-sensitive coloring composition contains a compound having a cyclic ether group, thereby accelerating the crosslinking of the [A] polymer or the like, and can further increase the hardness of the obtained pattern, and the radiation sensitivity of the radiation- .

As the compound having a cyclic ether group, a compound having two or more epoxy groups (oxirane group, oxetanyl group, etc.) in the molecule is preferable.

As the compound having two or more oxiranyl groups in the molecule, for example,

Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglyme Bisphenol-type diglycidyl ethers such as cidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as cidyl ether;

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;

Epoxidized soybean oil, and epoxidized linseed oil. These cyclic ether group-containing compounds may be used singly or in combination of two or more kinds.

Examples of the compound having a cyclic ether group having two or more oxetanyl groups in the molecule include isophthalic acid bis [(3-ethyloxetan-3-yl) methyl], 1,4-bis [ (3-ethyl-3-oxetanylmethyl) benzene, di [1-ethyl- (3-oxetanyl) methyl] (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) (3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyloxetane) (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether , Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethoxy) butane, xylenebisoxetane, 1 (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexaquis -Ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Bisphenol (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 and EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

The lower limit of the content of the cyclic ether group-containing compound is preferably 0.5 part by mass, more preferably 1 part by mass, further preferably 10 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is usually 150 parts by mass, preferably 100 parts by mass, more preferably 50 parts by mass, further preferably 25 parts by mass. When the content of the compound having a cyclic ether group is within the above range, the hardness of the obtained pattern can be further increased.

<Surfactant>

The surfactant is a component for enhancing the film-forming property of the radiation-sensitive coloring composition. The radiation sensitive coloring composition can improve the surface smoothness of the coating film by containing a surfactant, and as a result, the film thickness uniformity of the resulting pattern (cured film) can be improved.

Examples of the surfactant include fluorine surfactants and silicone surfactants. These surfactants may be used singly or in combination of two or more kinds.

The lower limit of the content of the surfactant is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is usually 3 parts by mass, preferably 2 parts by mass, more preferably 1 part by mass. When the content of the surfactant is within the above range, the uniformity of the film thickness of the formed coating film can be further improved.

<Adhesion preparation>

The adhesion assistant is a component for improving adhesion between a pattern forming object such as a substrate and a pattern (cured film). The adhesion aid 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 aid, a functional silane coupling agent is preferred. 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 aids may be used alone or in combination of two or more. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Methoxysilane and the like. Among them, examples of the functional silane coupling agent include? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma -methacryloxypropyltrimethoxysilane is preferable.

The lower limit of the content of the adhesion promoter is preferably 0.5 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is usually 30 parts by mass, preferably 20 parts by mass, more preferably 10 parts by mass. By setting the content of the adhesion aid within the above range, the adhesion between the formed pattern and the substrate is further improved.

<Dispersant>

By using a dispersant and a dispersion aid to be described later, the dispersion stability of [C] colorant and the like can be enhanced. As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic and nonionic ones can be used, but a polymer dispersing agent is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like.

These dispersants are commercially available and include, for example, acrylic copolymers such as "Disperbyk-2000", "Disperbyk-2001", "BYK-LPN6919", "BYK-LPN21116" Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, SOLSPERSE 76500 &quot; manufactured by JSR Corporation, &quot; SOL SPRUS 24000 &quot; manufactured by Lubrizol Corporation as a polyethyleneimine, AJISPER-PB821 manufactured by Ajinomoto Fine Techno Co., -PB822 &quot;, &quot; Ajisper-PB880 &quot;, and the like.

These dispersants may be used alone or in combination of two or more.

The lower limit of the content of the dispersant is preferably 1 part by mass, more preferably 10 parts by mass, per 100 parts by mass of the [C] colorant (solid content). On the other hand, the upper limit is usually 100 parts by mass, preferably 70 parts by mass, more preferably 50 parts by mass. If the content of the dispersing agent is too large, there is a possibility that developability and the like are damaged.

&Lt; Dispersing agent &

Examples of the dispersing aid include pigment derivatives, specifically, copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersing aid can be suitably determined within a range not hindering the object of the present invention.

&Lt; Preparation method of a radiation-sensitive coloring composition &gt;

The radiation-sensitive coloring composition is usually prepared by dissolving or dispersing the [A] polymer, the [B] photopolymerization initiator, the [C] colorant and, if necessary, other optional components in a solvent. The dispersion may be prepared by preparing a dispersion containing [C] a colorant, a dispersant, a solvent (dispersion medium) and the like, and then mixing the dispersion with other components.

<Solvent>

The solvent is suitably used so that each component in the radiation-sensitive coloring composition is uniformly dissolved or dispersed and does not react with each component. Examples of 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, aromatic hydrocarbons , Ketones, and other esters. As the solvent, a solvent described in JP-A-2011-232632 can be used.

&Lt; Method of Forming Coloring Pattern &gt;

Such a radiation-sensitive coloring composition is preferable for forming a pattern (cured film) of a liquid crystal display element. In addition, the present invention preferably includes a coloring pattern formed from the radiation-sensitive coloring composition.

The method for forming a coloring pattern of the present invention is characterized in that,

(1) a step of forming a coating film on a substrate using the radiation sensitive coloring 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) heating the developed coating film.

According to the forming method of the present invention, it is possible to form a coloring pattern for a display element in which contamination of the liquid crystal layer is suppressed and which has excellent voltage holding ratio and the like. Hereinafter, each process will be described in 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 coloring 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, resin substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide .

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

When a coating film is formed by a coating method, a coating film can be formed by applying a solution of the radiation-sensitive coloring composition on the transparent conductive film, and then preferably heating (prebaking) the coating surface. The solid content concentration of the composition solution used in the coating method is preferably 5 mass% or more and 50 mass% or less. Examples of the application method of the radiation sensitive coloring composition include a spraying method, a roll coating method, a rotary coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, Method can be adopted. Among them, the spin coating method and the slit coating method are preferable.

The conditions for the pre-baking vary depending on the kind of each component, the mixing ratio, and the like, but are about 70 ° C or more and 120 ° C or less and about 1 minute or more and about 15 minutes or less. The average film thickness of the coating film after prebaking is preferably 0.5 탆 or more and 10 탆 or less.

[Step (2)]

In this step, at least a part of the formed coating film is irradiated with radiation. At this time, when irradiating only a part of the coated film, for example, a method of irradiating with a photomask having a predetermined pattern may be employed.

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

The lower limit of the irradiation dose (exposure dose) is preferably 100 J / m 2, preferably 200 J / m 2, as measured by a light meter (OAI model 356, manufactured by Optical Associates Inc.) Is more preferable. The upper limit is preferably 5,000 J / m 2, more preferably 3,000 J / m 2.

[Step (3)]

In this step, unnecessary portions are removed by developing the coated film after irradiation with radiation to form a predetermined pattern. Examples of the developing solution used in the 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. have. To the aqueous solution of the alkaline compound, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added.

As the developing method, any of a puddle method, a dipping method, and a shower method may be used, and the developing time is preferably 10 seconds or more and 180 seconds or less at room temperature. Following the developing treatment, for example, water washing is carried out for about 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen to obtain a desired pattern.

[Step (4)]

In this step, the resulting patterned coating film is heated with a suitable heating apparatus such as a hot plate or an oven to obtain a cured film for a display element (coloring pattern). The heating temperature is about 100 ° C or more and 250 ° C or less. The heating time is, for example, from 5 minutes to 30 minutes on a hot plate, and from 20 minutes to 180 minutes in an oven.

<Manufacturing Method of Display Element>

In the present invention, a liquid crystal display element having such a coloring pattern is also suitably included. As a method for producing a liquid crystal display element, a pair of transparent substrates (transparent electrodes) having a transparent conductive film (electrode) on one surface thereof are first prepared, and a transparent conductive film A spacer, a protective film, or both are formed according to the above-described method. Then, an alignment film having a liquid crystal aligning ability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These substrates were placed face to face with a certain gap (cell gap) so that the liquid crystal alignment directions of the respective alignment films were orthogonal or anti-parallel with the side of the side on which the alignment film was formed as the inside, The liquid crystal serving as the liquid crystal layer is filled in the cell gap defined by the spacer, and the filling hole is sealed to constitute the liquid crystal cell. The liquid crystal display element of the present invention is obtained by joining a polarizing plate on both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one side of the substrate.

As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film or a spacer, and an orientation film are formed is prepared in the same manner as the above method. Thereafter, an ultraviolet curable sealant is applied using a dispenser along the edge of one of the substrates, and liquid crystal serving as a liquid crystal layer is dropped in a microdroplet using a liquid crystal dispenser, and bonding of both substrates is performed under vacuum. Then, ultraviolet rays are irradiated to the seal portion using a high-pressure mercury lamp, and both substrates are sealed. Finally, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain the liquid crystal display element of the present invention.

Examples of the liquid crystal used in each of the above methods include a nematic liquid crystal and a smectic liquid crystal. As the polarizing plate used for the outside of the liquid crystal cell, a polarizing plate in which a polarizing film called &quot; H film &quot;, in which iodine is absorbed, in which polyvinyl alcohol is stretched and oriented is sandwiched by a cellulose acetate protective film, .

(Example)

Hereinafter, the present invention will be described concretely with reference to Examples, but the present 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)]

Was measured by gel permeation chromatography (GPC) under the following conditions.

Device: "GPC-101" of Showa Denko

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

&Lt; Synthesis of Polymer &

[Synthesis Example 1] (A-1) Synthesis of an alkali-soluble resin having a methacryl group in a side chain

4 parts by mass of 2,2'-azobisisobutyronitrile and 300 parts by mass of diethylene glycol methyl ethyl ether were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, and 23 parts by mass of methacrylic acid, 10 parts by mass of styrene, 32 parts by mass of benzyl acrylate, 35 parts by mass of methyl methacrylate and 2.7 parts by mass of? -Methylstyrene dimer as a molecular weight regulator were added. Subsequently, while the solution was gently stirred, the temperature of the solution was raised to 80 DEG C, the temperature was maintained (maintained) for 4 hours, and the temperature was raised to 100 DEG C, (Solid content concentration = 24.9 mass%). The Mw of the obtained copolymer was 12,500. Subsequently, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 part by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 占 폚 for 30 minutes in an air atmosphere. Then, glycidyl methacrylate 16 (A-1) was obtained (solid content concentration = 29.0% by mass) by reacting the mixture at 90 占 폚 for 10 hours. The Mw of the copolymer (A-1) was 14,200. Re-precipitation purification was carried out by dropping the copolymer (A-1) into hexane, and the reaction rate of glycidyl methacrylate was calculated by ¹ H-NMR analysis of the resolidified resin solid content. The ratio of the peak derived from the methacryl group of glycidyl methacrylate to the proton of the aromatic ring near 6.8 ppm to 7.4 ppm derived from the structural unit of the copolymer of benzyl methacrylate at about 6.1 ppm and around 5.6 ppm From the comparison, the reaction rate of glycidyl methacrylate with 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 an epoxy group in side chain

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were fed into a flask equipped with a condenser and a stirrer. 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? -Methylstyrene dimer were charged, To start stirring. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2).

&Lt; Synthesis of binder resin &gt;

A cooling tube and a stirrer, 3 parts by mass of 2,2'-azobisisobutyronitrile and 235 parts by mass of propylene glycol monomethyl ether acetate were fed. Then, 20 parts by mass of methacrylic acid, 50 parts by mass of N-phenylmaleimide 12 mass parts of benzyl methacrylate, 10 mass parts of styrene, 15 mass parts of 2-hydroxyethyl methacrylate, 29 mass parts of 2-ethylhexyl methacrylate, and 5 mass parts of? -Methylstyrene dimer (chain transfer agent) Mass portion was charged, and the atmosphere was replaced with nitrogen. Thereafter, while gently stirring, the temperature of the reaction solution was raised to 80 占 폚, and the temperature was maintained and polymerized for 3 hours. Thereafter, the reaction solution was heated to 100 占 폚, and 0.5 part by mass of 2,2'-azobisisobutyronitrile was added, and the polymerization was further continued for 1 hour to obtain a binder resin (c-1) as a copolymer &Lt; / RTI &gt;

&Lt; Preparation of pigment dispersion &gt;

The compound represented by the formula (4) (wherein R ¹ to R ¹⁰ are hydrogen atoms) and the compound represented by the formula (5) (R ¹¹ to R ²⁰ are hydrogen atoms) as the [C] coloring agent (black pigment) , 5 parts by mass of an acrylic copolymer (BYK-LPN21116, manufactured by BYK) as a dispersant, 5 parts by mass of a binder resin (c-1) as a polymer, and 15 parts by mass of propylene glycol monomethyl And 75 parts by mass of ether acetate (PGMEA) were mixed with a bead mill to prepare a pigment dispersion (C-1).

[Examples 1 to 6 and Comparative Examples 1 to 4] <Preparation of radiation-sensitive coloring composition>

A pigment dispersion containing a solution (polymer solution) containing a polymer [A], a photopolymerization initiator [B], a pigment dispersion containing [C] a colorant, and a [D] thiol compound and a [ E] polyfunctional acrylate, and 0.2 parts by mass of a silicone surfactant ("SH8400FLUID" manufactured by Toray Dow Corning Silicone Co., Ltd.) were mixed. In addition to this mixture, propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content concentration became 25 mass%, to prepare a radiation-sensitive coloring composition.

And &quot; - &quot; in Table 1 indicate that they are not blended.

The symbols in Table 1 are as follows.

[A] Polymer (Polymer solution)

A-1: An alkali-soluble resin (solid concentration: 40% by mass) having a methacrylic group in the side chain obtained in Synthesis Example 1,

A-2: An alkali-soluble resin (solid concentration: 40% by mass) having an epoxy group in the side chain obtained in Synthesis Example 2

A-3: Codo resin having acryloyl group and carboxy group ("OGSOL CR-1030" manufactured by Osaka Gas Chemical Co., Ltd.) (solid concentration: 50% by mass)

A-4: acid-modified epoxy acrylate resin ("ZCR-1797H", manufactured by Nippon Kayaku Co., Ltd.) (solid concentration: 65%

[B] Photopolymerization initiator

b-1: 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ("Irgacure (registered trademark) OXE01"

b-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Registered trademark) OXE02 &quot;

B-3: Compound represented by the following formula

[C] Colorant

C-1: Pigment dispersion

[D] thiol compound

D-1: pentaerythritol tetrakis (3-mercaptopropionate)

D-2: Pentaerythritol tetrakis (3-mercaptobutyrate) ("Karenz MTPE1" manufactured by Showa Denko KK)

[E] polyfunctional acrylate

E-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

<Characteristic evaluation>

Using the radiation-sensitive coloring compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4, the following characteristics were evaluated.

&Lt; Formation of cured film &

The radiation sensitive coloring compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were applied to a glass substrate ("Corning (registered trademark) 7059" manufactured by Corning Inc.) using a spinner, Followed by pre-baking at 90 DEG C for 2 minutes to form a coating film. After these substrates were cooled to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was irradiated onto each coating film at an exposure amount of 1,000 J / m 2 using a high-pressure mercury lamp without interposing a photomask (Hereinafter also referred to as &quot; exposure &quot;). Subsequently, a showering phenomenon was carried out on these substrates for 60 seconds by discharging a developer composed of 0.04 mass% aqueous potassium hydroxide solution at 23 占 폚 at a developing pressure of 1 kgf / cm2 (nozzle diameter of 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 캜 for 30 minutes to form a cured film for evaluation having a film thickness of 3.0 탆 after post-baking.

<Evaluation of HPLC>

This cured film was cut into a powder form, mixed with a liquid crystal ("MLC6608" manufactured by Merck Ltd.), and then heated at 120 ° C for 60 minutes to elute the impurities in the cured film into liquid crystals. Thereafter, the cured film in the liquid crystal was removed by filtration using a PTFE filter to obtain a liquid crystal extract solution. The liquid crystal extract was diluted 100-fold with THF and analyzed using &quot; LC / MS6130 &quot; (column: Capcelpak C18, developing solvent: methanol) manufactured by Agilent Technologies. The charts of the liquid crystal extract and the liquid crystal were compared and it was judged that there was an elution of impurities when there was a peak only in the liquid crystal extract.

<Voltage Conservation Rate VHR>

A composition for forming an alignment film ("AL65008" manufactured by JSR Corporation) was formed on a soda glass substrate on which an SiO ₂ film was formed to prevent elution of sodium ion on the surface and further an ITO (indium-tin oxide alloy) ) Was applied using a spinner. Thereafter, the film was prebaked on a hot plate at 90 DEG C for 2 minutes, and further baked in a 200 DEG C clean oven for 30 minutes to form a 100 nm thick coating film. Subsequently, a bead spacer having a diameter of 5.5 占 퐉 was dispersed on the substrate having this alignment film, and a soda glass substrate having only ITO electrodes deposited in a predetermined shape on the surface thereof was opposed to the substrate. Glass beads were mixed. After injecting the liquid crystal extract solution described above, the liquid crystal injection port was sealed to produce a liquid crystal cell. The liquid crystal cell was placed in a constant temperature layer at 60 占 폚 and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage preservation rate measuring system ("VHR-1A type" manufactured by Toyotec Corporation). 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 formula. As the value of the voltage holding ratio is lower, the liquid crystal cell can not store and maintain the applied voltage at a predetermined level for 16.7 milliseconds, meaning that the liquid crystal can not be aligned sufficiently, and there is a high possibility of causing "burn-in"

Voltage Conservation Rate (%) = (Potential difference of liquid crystal cell after 16.7 milliseconds from the time of reference) / (Voltage applied at 0 milliseconds) 占 100

As shown in Table 1, in the cured films obtained from the radiation sensitive coloring compositions of Examples 1 to 6, there was no HPLC peak and elution into liquid crystals was not confirmed. It was also confirmed that the liquid crystal display elements obtained using the radiation sensitive coloring compositions of Examples 1 to 6 had a high voltage holding ratio.

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

Claims (9)

polymer,
A photopolymerization initiator having two or more sites represented by the following formula (1) in one molecule,
A lactam structure, an isomeric ring structure, or a combination thereof
A radiation-sensitive coloring composition comprising:

(In the formula (1), R ^X represents a monovalent organic group). The method according to claim 1,
Wherein the coloring agent has at least one of a site represented by the following formula (2) and a site represented by the following formula (3).

3. The method of claim 2,
Wherein the coloring agent is at least one of a coloring agent represented by the following formula (4) and a coloring agent represented by the following formula (5):

(Wherein 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 fluoride group having 1 to 6 carbon atoms ;
R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ each independently represent 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, SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ; Groups bonded to adjacent carbon atoms of R ² to R ⁵ , R ⁷ to R ¹⁰ , R ¹² to R ¹⁵ and R ¹⁷ to R ²⁰ may be bonded to each other directly or by -O-, -S-, -NH- or - NR ²¹ - and may form a cyclic structure together with the carbon atom to which they are bonded;
R ²¹ and R ²² each independently represent 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 the carbon-carbon bonds of these groups, and the hydrogen having the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group and alkynyl group some or all of the atoms, 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 ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ , an aralkyl group having 7 to 12 carbon atoms, 11 heteroaryl group or an aryl group having 6 to 12 carbon atoms, It may be good; Some or all of the aralkyl group, a heteroaryl group, and hydrogen atom having an aryl group, the 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, SR ²³ , SOR ²³ , SO ₂ R ²³ , SO ₃ R ²³ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ²³ or SO ₂ NR ²³ R ²⁴ Good;
R ²³ and R ²⁴ are, each independently, an alkyl group, a benzyl group or a phenyl group having a carbon number of 1~6, R ²³ and R ²⁴ are, directly or -O-, -S-, -NH- or -NR ²⁵ - the And may form a cyclic structure together with the atoms to which they are bonded;
R &lt; ²⁵ &gt; is a monovalent organic group). The method according to claim 1,
Wherein the polymer has a cyclic ether group, a (meth) acryloyl group, a vinyl group, or a combination thereof. The method according to claim 1,
Wherein the photopolymerization initiator is a photopolymerization initiator represented by the following formula (6):

(In the formula (6), two R &^lt; ^1A &gt; independently represent 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, , A 2-thienyl group, a 2-thenyl group, a phenyl group or a naphthyl group, and a part or all of the hydrogen atoms of the phenyl group or the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, It may be good;
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 represents 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-thienyl 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 represents a hydrogen atom, a methyl group, an alkyl group having 2 to 12 carbon atoms, a phenyl group, or a naphthyl group, and a part or all of the hydrogen atoms of the alkyl group having 2 to 12 carbon atoms may be substituted with a carboxyl group, a methoxycarbonyl group, An acyloxy group having 1 to 6 carbon atoms, a benzoyloxy group or an acyl group having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms of the phenyl group or the 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;
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 the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group of 1 to 6 carbon atoms or a halogen atom). 6. The method according to any one of claims 1 to 5,
Sensitive coloring composition for forming a coloring pattern of a liquid crystal display element. A step of forming a coating film on a substrate using the radiation sensitive coloring composition according to claim 6,
A step of irradiating a part of the coating film with radiation,
A step of developing the coated film irradiated with the radiation,
And heating the developed coating film. A colored pattern formed by the radiation sensitive coloring composition according to claim 6. 9. A liquid crystal display element comprising the coloring pattern according to claim 8.