JP5003200B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for colored layer formation and the like which generate neither development residue nor scum on a pattern edge in development, cause neither chipping of a pattern edge nor undercut even with a low exposure amount, and can give a fine pattern. <P>SOLUTION: The radiation-sensitive composition for colored layer formation comprises (A) a colorant, (B) an alkali-soluble resin comprising a polyester having an aromatic cyclic hydrocarbon skeleton in a main chain and a polymerizable unsaturated bond in a side chain, (C) a polyfunctional monomer and (D) a photoradical generator. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display element. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a radiation-sensitive composition used for forming a colored layer useful for production, a color filter having a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, in the technical field of color filters, the trend to shorten the tact time by lowering the exposure amount has become the mainstream, and the formation of finer patterns reflecting the higher definition of liquid crystal display elements. However, with conventional colored radiation-sensitive compositions, pattern edges are easily chipped and undercut during development, so that pixels with a good pattern shape and a black matrix are obtained while shortening the tact time. However, it was not always sufficient in terms of forming a high-definition pattern.

JP-A-2-144502 JP-A-3-53201

  The problem of the present invention is that the radiation-sensitive composition for forming a colored layer exhibiting excellent developability, more specifically, no undissolved material remains during development or scum is generated at the pattern edge, Another object of the present invention is to provide a radiation-sensitive composition for forming a colored layer that does not cause chipping or undercut of pattern edges even at a low exposure amount, and gives a fine pixel pattern and black matrix pattern.

The present invention, first,
A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photoradical generator, wherein (B) the alkali-soluble resin The aromatic ring in the main chain has an aromatic hydrocarbon skeleton selected from the group of naphthalene ring, 2,2′-binaphthyl ring, biphenylene ring, acenaphthylene ring, acenaphthene ring, phenanthrene ring, anthracene ring or perylene ring , And a radiation-sensitive composition for forming a colored layer, comprising a polyester having a polymerizable unsaturated bond in the side chain.
The “aromatic hydrocarbon skeleton” as used in the present invention does not include a hydrocarbon skeleton having a ring structure composed only of carbon atoms that do not constitute an aromatic ring.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

The present invention secondly,
The color filter which has a colored layer formed using the said radiation sensitive composition for colored layer formation.

Third, the present invention
A color liquid crystal display device comprising the color filter;

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer- component (A)-
The color tone of the colorant, which is the component (A) in the present invention, is not particularly limited, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Organic pigments or inorganic pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colourists, Inc.), and compounds having a color index (CI) number as shown below can be mentioned.

CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ...... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175, C.I Pigment Yellow 180, C.I Pigment Yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73;
CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97,

CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, C.I. Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Brown 23, CI Pigment Brown 25;
CI Pigment Black 1, CI Pigment Black 7.
The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

  Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  In the present invention, the pigments can be used alone or in admixture of two or more, and an organic pigment and an inorganic pigment can be used in combination. The above organic pigments are used, and when forming a black matrix, two or more organic pigments and / or carbon black are preferably used.

In the present invention, the pigment surface can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in Patent Document 3 and the like, and various commercially available polymers or oligomers for dispersing pigments.
JP-A-8-259876

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). MegaFuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (above Asahi Glass Co., Ltd.), BYK, Disperbyk (above, Big Chemie Japan Co., Ltd.) Product), Solsperse (manufactured by Seneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals Beebuy Co., Ltd.), and the like.
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

  In the present invention, the radiation-sensitive resin composition can be prepared by an appropriate method. However, when a pigment is used as a colorant, the pigment is used in a solvent in the presence of a dispersant, as will be described later (B ) Along with alkali-soluble resin, for example, using a bead mill, roll mill, etc., mixing and dispersing while pulverizing to prepare a pigment dispersion, which is prepared by mixing with components (B) to (D) described later Is preferred.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of the pigment. Preferably it is 10-50 weight part. In this case, if the amount of the dispersant used exceeds 100 parts by weight, developability and the like may be impaired.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 200 to 1,200 parts by weight, preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent and a dispersant is used. Preferably, it can be carried out by mixing and dispersing while cooling with cooling water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixed solution is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.
Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 10 ⁸ dyn / sec. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(B) component-
The component (B) in the present invention is an aromatic ring in which the aromatic ring is selected from the group consisting of naphthalene ring, 2,2′-binaphthyl ring, biphenylene ring, acenaphthylene ring, acenaphthene ring, phenanthrene ring, anthracene ring or perylene ring in the main chain. An alkali-soluble resin (hereinafter referred to as “(B) alkali-soluble”) having a polyester having a hydrocarbon skeleton and having a polymerizable unsaturated bond in the side chain (hereinafter referred to as “side-chain unsaturated aromatic cyclic polyester”). (A) a resin that acts as a binder for the colorant and is soluble in an alkaline developer used in the development processing step when producing a color filter.

As the aromatic ring in the aromatic hydrocarbon skeleton constituting the main chain in the side chain unsaturated aromatic cyclic polyester, a 2,2′-binaphthyl ring, a phenanthrene ring, an anthracene ring and the like are particularly preferable.
In the side chain unsaturated alicyclic polyester, the structural part having an aromatic hydrocarbon skeleton is usually connected by two bonds to form a main chain, and the two bonds are aromatic hydrocarbons. It can exist in an appropriate position in the structural part having a skeleton.

The aromatic ring in the aromatic cyclic hydrocarbon skeleton can have one or more substituents such as a halogen atom and a monovalent hydrocarbon group having 1 to 20 carbon atoms, for example.
As a halogen atom which makes the said substituent, a fluorine atom, a chlorine atom, etc. can be mentioned, for example.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms forming the substituent include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, Aliphatic hydrocarbon groups such as n-hexyl group and n-octyl group; cycloaliphatic hydrocarbon groups such as cyclopentyl group and cyclooctyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl And aromatic cyclic hydrocarbon groups such as groups.

  The polymerizable unsaturated bond of the side chain in the side chain unsaturated alicyclic polyester is used as a later-described (C) polyfunctional monomer or in some cases when the radiation-sensitive composition for forming a colored layer is used. Although it is not particularly limited as long as it can be copolymerized with a monofunctional monomer, it is, for example, (meth) acrylic acid from the viewpoint of ease of synthesis and copolymerization of the side chain unsaturated alicyclic polyester. An unsaturated bond derived from crotonic acid, maleic acid, fumaric acid, itaconic acid and the like is preferable, and an unsaturated bond derived from (meth) acrylic acid is particularly preferable.

  The side chain unsaturated aromatic cyclic polyester in the present invention is particularly preferably a polyester represented by the following formula (1) (hereinafter referred to as “polyester (1)”).

[In the formula (1), each X independently represents a divalent group represented by the following formula (3), formula (4) or formula (5), and each Y independently represents a carboxyl group. 4 represents a residue excluding a carboxyl group of an organic compound having four, each R ¹ independently represents a hydrogen atom or a methyl group, and each R ² independently represents a hydrogen atom or a carboxyl group blocking agent residue. N is an integer of 1-40. However, the two bonds marked with * in the formula are directly connected to each other.

（但し、Ｒ³ およびＲ⁴ は相互に独立に炭素数１〜２０の１価の炭化水素基を示し、複数存在するＲ³ およびＲ⁴ はそれぞれ相互に同一でも異なってもよく、ｐは０〜４の整数であり、ｑは０〜４の整数である。）

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and p is 0 -4 is an integer, and q is an integer of 0-4.)

（但し、Ｒ³ およびＲ⁴ は相互に独立に炭素数１〜２０の１価の炭化水素基を示し、複数存在するＲ³ およびＲ⁴ はそれぞれ相互に同一でも異なってもよく、ｐは０〜４の整数であり、ｑは０〜４の整数である。）

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and p is 0 -4 is an integer, and q is an integer of 0-4.)

（但し、Ｒ³ およびＲ⁴ は相互に独立に炭素数１〜２０の１価の炭化水素基を示し、複数存在するＲ³ およびＲ⁴ はそれぞれ相互に同一でも異なってもよく、ｒは０〜６の整数であり、ｓは０〜６の整数である。）〕

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and r is 0 ) Is an integer of -6, and s is an integer of 0-6.)]

  The side chain unsaturated aromatic cyclic polyester is prepared, for example, by synthesizing a diol compound having an aromatic hydrocarbon skeleton in the main chain and a polymerizable unsaturated bond in the side chain. It can be produced by an esterification reaction with an acid anhydride of a polyvalent carboxylic acid having a valence of at least 2, preferably 2 to 4, and particularly preferably a tetravalent carboxylic acid.

  The polyester (1) is preferably represented by the di (meth) acryloyl group-containing diol compound represented by the following formula (9), formula (10) or formula (11), and the following formula (12). It can be produced by an esterification reaction with a tetrabasic acid dianhydride (hereinafter referred to as “tetrabasic acid dianhydride (12)”).

〔式（９）において、Ｒ¹ 、Ｒ³ 、Ｒ⁴ 、ｐおよびｑは式（１）におけるそれぞれＲ¹ 、Ｒ³ 、Ｒ⁴ 、ｐおよびｑと同義である。〕

In [Equation ^{(9), R 1, R} 3, R 4, p and q have the same meanings as respectively ^{R 1, R 3, R 4} , p and q in the formula (1). ]

〔式（１０）において、Ｒ¹ 、Ｒ³ 、Ｒ⁴ 、ｐおよびｑは式（１）におけるそれぞれＲ¹ 、Ｒ³ 、Ｒ⁴ 、ｐおよびｑと同義である。〕

In [Equation ^{(10), R 1, R} 3, R 4, p and q have the same meanings as respectively ^{R 1, R 3, R 4} , p and q in the formula (1). ]

〔式（１１）において、Ｒ¹ 、Ｒ³ 、Ｒ⁴ 、ｐおよびｑは式（１）におけるそれぞれＲ¹ 、Ｒ³ 、Ｒ⁴ 、ｒおよびｓと同義である。〕

[In the formula (11), R ¹ , R ³ , R ⁴ , p and q are the same as R ¹ , R ³ , R ⁴ , r and s in the formula (1), respectively. ]

〔式（１２）において、Ｙは式（１）におけるＹと同義である。〕

[In Formula (12), Y is synonymous with Y in Formula (1). ]

Below, the manufacturing method of side chain unsaturated aromatic cyclic polyester is demonstrated centering on the case of polyester (1).
First, as the di (meth) acryloyl group-containing diol compound, for example, a diphenol compound corresponding to X represented by the formula ( 3 ) , formula (4) or formula (5) is used, and this is converted to diglycidyl ether. The diglycidyl etherified product can be synthesized by adding acrylic acid and / or methacrylic acid to the epoxy groups at both ends of the diglycidyl etherified product.

When synthesizing the (meth) acryloyl group-containing diol compound, the diphenol compounds can be used alone or in admixture of two or more.
The di (meth) acryloyl group-containing diol compound thus obtained preferably has an acid value of less than 10 mgKOH / g and an epoxy equivalent in the range of 10,000 to 20,000.

The diglycidyl etherification reaction of a diphenol compound when synthesizing a di (meth) acryloyl group-containing diol compound can be carried out according to a general epoxy resin synthesis method. For example, a basic catalyst for a diphenol compound can be used. Can be synthesized by reacting epichlorohydrin in the presence of.
The diglycidyl etherified product thus obtained preferably has an epoxy equivalent in the range of 260 to 300.

  Further, the tetrabasic acid dianhydride (12) is not particularly limited, but is preferably a compound represented by the following formula (12-1) or a compound represented by the formula (12-2). And compounds represented by formula (12-3).

  The method for carrying out the esterification reaction between the di (meth) acryloyl group-containing diol compound and the tetrabasic acid dianhydride (12) in producing the polyester (1) is not particularly limited. A polyester (1) can be produced by dissolving a (meth) acryloyl group-containing diol compound in an organic solvent under heating, adding tetrabasic acid dianhydride (12) to this, and reacting with stirring. it can.

In the polyester (1) obtained by such esterification reaction, R ² in the formula (1) is all hydrogen atoms, and 2 to 3 are present in each residue portion of the tetrabasic acid dianhydride (12). And thus exhibit excellent solubility in an alkaline developer.

In the present invention, at least a part of the free carboxyl groups in the polyester (1) obtained by the esterification reaction can be used by blocking with a carboxyl group blocking agent. In this case, the carboxyl group is blocked. By changing the ratio, the acid value of the polyester (1) can be adjusted to control the solubility in an alkali developer.
The carboxyl group blocking agent is not particularly limited, and examples thereof include known ones such as glycidyl ethers and carbodiimides. For example, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, resorcing licidyl ether and the like. Is preferred.

  In the present invention, the weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) (elution solvent: tetrahydrofuran) of polyester (1) is preferably 3,000 to 100,000. 000, more preferably 5,000 to 25,000. In this case, if the Mw of the polyester (1) is smaller than the above range, the flexibility of the coating and the adhesion to the substrate tend to be lowered. On the other hand, if the Mw is larger than the above range, the curability at the time of exposure, the uncured state There is a tendency that the solubility in an alkali developing solution is reduced. The Mw of the polyester (1) can be adjusted by changing the amount of the organic solvent or reaction raw material in the esterification reaction.

In the present invention, the acid value of the polyester (1) is preferably in the range of 20 to 80 mgKOH / g, more preferably 30 to 70 mgKOH / g. Although depending on the kind of tetrabasic acid dianhydride (12), it is preferable that 50% by mole or more, preferably 70% by mole or more of R ² in the polyester (1) is a hydrogen atom. It is desirable from the viewpoint of securing the property.
Moreover, it is preferable that the polyester (1) after blocking with a carboxyl group blocking agent has an epoxy equivalent of 60,000 or more.

Since the polyester (1) has a plurality of polymerizable acryloyl groups or methacryloyl groups, the polyester (1) is cured by exposure and hardly dissolves in an alkali developer. On the other hand, since it dissolves in an alkali developer in an uncured state, it is exposed partially as a resist film, leaving a cured portion, and developing an alkali developability that allows the uncured portion to be dissolved and removed with an alkali developer. Polyester (1) has good adhesion to various substrates, small curing shrinkage, high glass transition point (Tg) and excellent heat resistance, and can form a resist film with high hardness.
In the present invention, the side chain unsaturated aromatic cyclic polyester can be used alone or in admixture of two or more.

  Further, in the present invention, as the alkali-soluble resin, together with the side chain unsaturated aromatic cyclic polyester, a polyester having an alicyclic hydrocarbon skeleton in the main chain and a polymerizable unsaturated bond in the side chain (hereinafter, "Side-chain unsaturated alicyclic polyester") can be used in combination.

  Examples of the alicyclic hydrocarbon skeleton in the side chain unsaturated alicyclic polyester include cyclopentane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, i-propylcyclopentane, and 1-methyl-3-i. -Propylcyclopentane, cyclopentene, cyclohexane, methylcyclohexane, ethylcyclohexane, n-propylcyclohexane, i-propylcyclohexane, 1-methyl-3-i-propylcyclohexane, 1-methyl-4-i-propylcyclohexane, cyclohexene, cyclo Heptane, methylcycloheptane, ethylcycloheptane, n-propylcycloheptane, i-propylcycloheptane, 1-methyl-3-i-propylcycloheptane, 1-methyl-4-i-propylcycloheptane Emissions can cycloheptene, cyclooctane, a skeleton derived from a hydrocarbon having from 4 to 8 membered carbocyclic ring cyclooctene.

  Of these alicyclic hydrocarbon skeletons, skeletons having a cyclohexane ring are preferable, and skeletons derived from 1-methyl-3-i-propylcyclohexane, 1-methyl-4-i-propylcyclohexane and the like are particularly preferable.

  In the side chain unsaturated alicyclic polyester, the alicyclic hydrocarbon skeleton can form a main chain ester structure in which structural units of the polyester are linked directly or via a divalent linking group.

Examples of the divalent group include a methylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetrabutylene group, or a linear or branched alkylene group having 1 to 6 main chain carbon atoms; A cycloalkylene group having a 4- to 8-membered carbocyclic ring such as a butylene group, a cyclopentylene group, or a cyclohexylene group; a cyclopentylene methylene group, a cyclopentylene ethylene group, a cyclopentylene propylene group, a cyclohexylene methylene group, a cyclohexene group; A divalent hydrocarbon chain having 1 to 6 main carbon atoms such as a methylene group, an ethylene group or a propylene group is bonded to a cycloalkylene group having a 4- to 8-membered carbocyclic ring such as a silylene ethylene group or a cyclohexylene propylene group. Groups such as 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, etc. An arylene group having from 10 to 10 carbon atoms; a group in which a divalent hydrocarbon chain having 1 to 6 main carbon atoms such as a methylene group, an ethylene group or a propylene group is bonded to the arylene group having 6 to 10 carbon atoms; m-phenyleneoxy group _{(-m-C 6 H 4 -O} -), p- phenylene group _{(-p-C 6 H 4 -O-} ) arylene group having 6 to 10 carbon atoms such as; oxy in the arylene group Examples include groups in which a divalent hydrocarbon chain having 1 to 6 carbon atoms in the main chain such as a methylene group, an ethylene group, and a propylene group is bonded to the group.
Of these divalent groups, an aryleneoxy group having 6 to 10 carbon atoms is preferable, and a p-phenyleneoxy group is particularly preferable.

  The polymerizable unsaturated bond of the side chain in the side chain unsaturated alicyclic polyester is used as a later-described (C) polyfunctional monomer or in some cases when the radiation-sensitive composition for forming a colored layer is used. Although it is not particularly limited as long as it can be copolymerized with a monofunctional monomer, it is, for example, (meth) acrylic acid from the viewpoint of ease of synthesis and copolymerization of the side chain unsaturated alicyclic polyester. An unsaturated bond derived from crotonic acid, maleic acid, fumaric acid, itaconic acid and the like is preferable, and an unsaturated bond derived from (meth) acrylic acid is particularly preferable.

The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) of the side chain unsaturated alicyclic polyester (elution solvent: tetrahydrofuran) is usually 1,000-60, 000, preferably 2,000 to 25,000.
The side chain unsaturated alicyclic polyester preferably has an acid value in the range of 60 to 70 mgKOH / g from the viewpoint of securing good alkali developability in an uncured state.
In this invention, a side chain unsaturated alicyclic polyester can be used individually or in mixture of 2 or more types.

  Moreover, in this invention, other alkali-soluble resin can be used together with polyester (1) or a mixture of polyester (1) and a side chain unsaturated alicyclic polyester as alkali-soluble resin.

Examples of the other alkali-soluble resin include a polymerizable unsaturated monomer having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid, and another copolymerizable unsaturated monomer (hereinafter, “ And a copolymer with a "copolymerizable unsaturated monomer").

Examples of the polymerizable unsaturated monomer having a carboxyl group (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) include:
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the polymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methyl. Examples thereof include styrene, p-hydroxy-α-methylstyrene, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide and the like.
These polymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in admixture of two or more.
Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprene sulfonic acid and p-styrene sulfonic acid.
These polymerizable unsaturated monomers having a sulfonic acid group can be used alone or in admixture of two or more.

As the copolymerizable unsaturated monomer, for example,
Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc. (hereinafter simply referred to as “macromonomers”) :):
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methyl N-aryl maleimides such as phenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexylmaleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturated carboxylic esters such as (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Examples thereof include aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

  In the present invention, as other alkali-soluble resin, for example, a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter simply referred to as “carboxyl group-containing copolymer”). (B) polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl, (a) carboxyl group-containing unsaturated monomer having (meth) acrylic acid as an essential component At least one selected from the group of maleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate, and (c) optionally styrene, α-methylstyrene, methyl (meth) ) Acrylate, allyl (meth) acrylate and phenyl (meth) a Copolymers of at least one further monomer mixture comprising selected from the group of relations is more preferred.

The Mw of other alkali-soluble resins is usually 2,000 to 300,000, preferably 3,000 to 100,000.
In the present invention, other alkali-soluble resins can be used alone or in admixture of two or more.

In this invention, the total usage-amount of alkali-soluble resin is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the total use amount of the alkali-soluble resin is less than the above range, for example, the alkali developability may be lowered, or there is a possibility that background stains or film residue may occur on the substrate in the unexposed area or on the light shielding layer. On the other hand, if the above range is exceeded, the colorant concentration is relatively lowered, and it may be difficult to achieve the target color density as a thin film.
The proportion of the side chain unsaturated aromatic cyclic polyester in the alkali-soluble resin is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, and particularly preferably 40 to 100% by weight. In this case, if the use ratio of the side chain unsaturated aromatic cyclic polyester is less than the above range, the desired effect of the present invention may be impaired.

-(C) component-
The component (C) in the present invention is a polyfunctional monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, represented by the following formula (15) Compound represented by the following formula (16)

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than the above range, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds the above range, for example, alkali developability may be reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include those similar to the compounds exemplified for the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer in the other alkali-soluble resins, and N- (meta ) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

  The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, if the usage ratio of the monofunctional monomer is too large, the strength and surface smoothness of the resulting colored layer may be insufficient. The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is less than the above range, the strength and surface smoothness of the colored layer tend to decrease. On the other hand, if it exceeds the above range, for example, alkali developability decreases or There is a tendency that soiling, film residue, and the like are likely to occur on the substrate or the light shielding layer.

-(D) Photoradical generator-
The component (D) in the present invention comprises (C) a polyfunctional monomer and a monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray. It is a photo radical generator that generates radicals capable of initiating polymerization of the body.
Examples of the photo radical generator in the present invention include carbazole compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, and phosphine compounds. Examples thereof include compounds and triazine compounds, and among these, carbazole compounds are particularly preferable.

  Examples of the carbazole-based compound include a compound represented by the following formula (6) (hereinafter referred to as “carbazole-based compound (6)”) and a compound represented by formula (7) (hereinafter referred to as “carbazole-based compound”). (7) ")).

[In the formula (6), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). Show
R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ are present. R ⁹ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a carbon atom having 4 to 20 carbon atoms. A monovalent sulfur-containing heterocyclic group, and a plurality of R ⁹ may be the same or different from each other, a is an integer of 0 to 5, b is an integer of 0 to 5, and (a + b) ≦ 5 is there. ]

[In Formula (7), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). Show
R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ are present. R ⁹ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a carbon atom having 4 to 20 carbon atoms. A monovalent sulfur-containing heterocyclic group, and a plurality of R ⁹ may be the same or different from each other, c is an integer of 0 to 5, d is an integer of 1 to 5, and (c + d) ≦ 5 Yes, e is an integer of 0-6. ]

In Formula (6) and Formula (7), examples of the alkyl group having 1 to 20 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having a carbon number of R ⁵ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group.
In Formula (6) and Formula (7), R ⁵ is preferably, for example, a methyl group, an ethyl group, or the like.

In Formula (6) and Formula (7), examples of the alkyl group having 1 to 20 carbon atoms of R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Etc.
Moreover, as a C3-C8 cycloalkyl group of R < ⁶ > and R < ⁷ >, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned, for example.

Examples of the substituent for the phenyl group of R ⁶ and R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group. Group, an alkyl group having 1 to 6 carbon atoms such as n-hexyl group; a cycloalkyl group having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group: methoxy group, ethoxy group, n-propoxy group, i-propoxy group, an alkoxyl group having 1 to 6 carbon atoms such as an n-butoxy group and a t-butoxy group; a cycloalkyloxy group having 3 to 6 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group: a phenyl group; a fluorine atom, a chlorine atom, etc. A halogen atom etc. can be mentioned.

Examples of the monovalent alicyclic group having 7 to 20 carbon atoms of R ⁶ and R ⁷ (excluding the cycloalkyl group) include, for example, a group having a 1-alkylcycloalkane skeleton and a bicycloalkane skeleton. A group having a tricycloalkane skeleton, a group having a spiroalkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like.

In Formula (6) and Formula (7), R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group, an ethyl group, or the like.

In formula (6) and formula (7), examples of the alkyl group having 1 to 12 carbon atoms of R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having 3 to 8 carbon atoms R ^8, examples thereof include a cyclopentyl group, a cyclohexyl group.

As the alkoxyl group having 1 to 12 carbon atoms R ^8, for example, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, t-butoxy group, n- pentyloxy group, Examples include n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group and the like.
As the cycloalkyloxy group having 3 to 8 carbon atoms R ^8, for example, can be exemplified cyclopentyloxy, cyclohexyloxy group and the like.

In Formula (6) and Formula (7), R ⁸ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, an ethoxy group, or the like.

In formula (6) and formula (7), R ^{9 is} a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms and a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms. Examples of the group or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms include a thiolanyl group, an azepinyl group, a dihydroazepinyl group, a dioxolanyl group, a triazinyl group, an oxathianyl group, a thiazolyl group, an oxadiazinyl group, Xidodanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, Pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, iso Ndryl, benzofuranyl, benzothiophenyl, indolizinyl, chromenyl, quinolinyl, isoquinolinyl, purinyl, quinazolinyl, cinnolinyl, phthalazinyl, pteridinyl, carbazolyl, acridinyl, phenanthridinyl, Examples thereof include a thioxanthenyl group, a phenazinyl group, a phenothiazinyl group, a phenoxathinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.

In Formula (6) and Formula (7), R ⁹ is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.

  In the formula (6), a is preferably 0, 1 or 2, particularly preferably 1, and b is preferably 0 or 1, particularly preferably 0.

  In the formula (7), c is preferably 0, 1 or 2, particularly preferably 1, d is preferably 1, e is preferably 0, 1 or 2, and particularly preferably 1.

As a specific example of the carbazole compound (6),
1- [9-Ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate,

1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate,

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime)
Etc.

Specific examples of the carbazole compound (7) include
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime)
Etc.

  Of these carbazole compounds (6) and carbazole compounds (7), 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like are preferable, and in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazole-3-i]]-1- (O-acetyloxime) and the like are preferable.

  Examples of the biimidazole compound include compounds having at least one main skeleton represented by the following formula (17-1), formula (17-2), or formula (17-3).

Specific examples of biimidazole compounds include
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole is preferred, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. Imidazole is preferred.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as the photoradical generator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As such a hydrogen donor, a mercaptan compound defined below, an amine compound defined below, and the like are preferable.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1-3, more preferably 1-2 mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “mercaptan”). It is referred to as “system hydrogen donor”).
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In the amine-based hydrogen donor, at least one of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted group may be substituted at a position other than the amino group. Alternatively, it may be substituted with an unsubstituted phenoxycarbonyl group, nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples include ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
In addition, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone can act as a photoradical initiator alone even in the absence of a biimidazole compound. .

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothia A Lumpur / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.

Examples of the benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the xanthone compound include xanthone, thioxanthone, and 2-chlorothioxanthone.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Tyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, represented by the following formula (18) Compound represented by the following formula (19)

Examples thereof include compounds having a halomethyl group.
In the present invention, the photo radical generator can be used alone or in admixture of two or more.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking / sensitizer can be used in combination with the photoradical generator as necessary.

The amount of the photo radical generator used in the present invention is usually 0.01 to 200 with respect to (C) 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer optionally used. Part by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the amount of the photo radical generator used is less than the above range, curing by exposure becomes insufficient, and it may be difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds the above range, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed substrate or on the light shielding layer.
In the present invention, when a carbazole compound and another photoradical generator are used in combination as a photoradical generator, the usage ratio of the other photoradical generator is such that the carbazole compound and the other photoradical generator are used. Preferably it is 50 weight% or less with respect to the sum total, More preferably, it is 30 weight% or less.

-Additives-
The radiation-sensitive composition for forming a colored layer of the present invention can contain various additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (provided to improve the solubility characteristics of the radiation-sensitive composition in an alkaline developer and to further suppress the remaining undissolved product after development) The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when there is too much usage-amount of organic acid, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino- Mono (cyclo) alkanolamines such as 1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclo Di (cyclo) alkanolamines such as hexanol) amine;
Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 -Tri (cyclo) alkanolamines such as cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1, 2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the solvent described later, prevention of soiling and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, in particular 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when there is too much usage-amount of an organic amino compound, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono (Poly) alkylene glycol monoalkyl ether acetates such as ethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl Ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n-butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the liquid composition is usually from 5 to 5 from the viewpoint of applicability and stability of the obtained liquid composition. The amount is 50% by weight, preferably 10 to 40% by weight.

Color filter The color filter of this invention has a colored layer formed using the radiation-sensitive composition for colored layer formation of this invention.
Below, the method of forming the colored layer in the color filter of this invention is demonstrated.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using each liquid composition of the radiation-sensitive composition in which the green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate can be obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
The black matrix can be formed in the same manner as in the case of the pixel using, for example, a radiation-sensitive composition for forming a colored layer in which a black pigment is dispersed.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
Exposure of radiation is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one form of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed as described above on the thin film transistor substrate array using the radiation-sensitive composition for forming a colored layer of the present invention. By doing so, a color liquid crystal display element having particularly excellent characteristics can be produced.

The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are as follows. (D)
(B) At least one selected from the group of di (meth) acryloyl group-containing diol compounds represented by formula (9), formula (10) or formula (11) and tetrabasic acid (B) alkali-soluble resin A radiation-sensitive composition for forming a colored layer, comprising a polyester (1) having an Mw of 3,000 to 100,000, obtained by an esterification reaction with at least one selected from the group of dianhydrides (12).
(B) (C) The radiation sensitive material for forming a colored layer according to (a), wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Sex composition.
(C) (D) The photoradical generator is ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}-as a carbazole compound. 9. H. -Carbazol-3-yl] -1- (O-acetyloxime) The radiation-sensitive composition for forming a colored layer according to (i) or (b) above.
(D) (A) The radiation-sensitive composition for forming a colored layer according to (a), (b) or (c), wherein the colorant contains an organic pigment and / or carbon black.

Further, the preferred color filter of the present invention is
(E) It has a pixel and / or a black matrix formed by using the radiation sensitive composition for forming a colored layer of (i), (b), (c) or (d).

The preferred color liquid crystal display element of the present invention is
(F) comprising the color filter of (e),
Further preferred color liquid crystal display elements of the present invention are:
(G) The color filter described in (e) is provided on the thin film transistor substrate array.

The radiation-sensitive composition for forming a colored layer of the present invention does not leave undissolved material during development, does not cause scum at the pattern edge, and causes chipping and undercut of the pattern edge even at a low exposure amount. In addition, a fine pixel pattern and a black matrix pattern can be formed, and the pixel and the black matrix have high surface smoothness and excellent adhesion to the substrate.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Here, parts and% are based on weight.
<Manufacture of alkali-soluble resin>

Synthesis Example 1 (Production of polyester for reference )
A flask equipped with a condenser and a stirrer was charged with 1,000 g of 9,9-bis (4-hydroxyphenyl) fluorene, 1,320 g of epichlorohydrin and 1,470 g of dimethyl sulfoxide and heated to 50 ° C. while stirring. After dissolution, 250 g of caustic soda was added and reacted at 65 to 90 ° C. for 10 hours. The progress and end point of the reaction were confirmed by measuring the epoxy equivalent, and after completion of the reaction, the solvent was distilled off under reduced pressure at 90-100 ° C. Thereafter, the reaction product is redissolved in toluene at 50 to 70 ° C., further distilled water is added and the mixture is washed with water, and after standing separation, the organic layer is distilled off at 50 to 70 ° C. under reduced pressure. 1,160 g of diglycidyl etherified product was obtained.

  Next, 1,000 g of the obtained diglycidyl etherified product, 330 g of methacrylic acid, and 0.94 g of hydroquinone monomethyl ether were charged into a flask equipped with a condenser and a stirrer, and heated to 60 ° C. with stirring and dissolved. 7.55 g of tetraethylammonium bromide was added, and the reaction was continued by stirring at 70 to 90 ° C. After 15 hours, the acid value and epoxy equivalent were measured to confirm the end point of the reaction and cooled to room temperature to obtain 1,280 g of a dimethacryloyl group-containing diol compound.

Next, 700 g of the obtained dimethacryloyl group-containing diol compound and 1,300 g of methyl isobutyl ketone were charged into a flask equipped with a condenser and a stirrer, and dissolved by heating to 60 ° C. with stirring. The pyromellitic anhydride (made by Daicel Chemical Industries, Ltd.) 220g represented by -1) was added, and reaction was continued, stirring at 80 degreeC. After measuring the acid value and confirming the end point of the reaction, adding distilled water to the reaction solution, washing with water and performing stationary separation, the organic layer was distilled off at 50 to 70 ° C. under reduced pressure, 860 g of polyester was obtained. The obtained polyester had Mw = 18,000.
This polyester is a polyester in which X is 9,9-bis (4-hydroxyphenyl) fluorene residue, Y is pyromellitic anhydride residue, R ¹ is a methyl group, and R ² is a hydrogen atom in the formula (1). there were.

Synthesis Examples 2 to 4 (Production of polyester (1))
In Synthesis Example 1, each polyester (1) was prepared in the same manner as in Synthesis Example 1 except that 1,000 g of 9,9-bis (4-hydroxyphenyl) fluorene was changed to the raw material compounds and usage amounts shown in Table 1. Obtained.
The obtained polyesters (1) are successively referred to as “alkali-soluble resin (B-2)”, “alkali-soluble resin (B-3)” and “alkali-soluble resin (B-4)”.

Synthesis Example 5 (Production of alkali-soluble resin for comparison)
A flask equipped with a condenser and a stirrer was charged with 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate, followed by 12 parts of methacrylic acid, 18 parts of styrene, and benzyl methacrylate. 24 parts, 30 parts of N-phenylmaleimide, 16 parts of 2-hydroxyethyl methacrylate, and 6.5 parts of α-methylstyrene dimer as a chain transfer agent were substituted with nitrogen, and then gently stirred to prepare a reaction solution of 80 parts. The mixture was heated to 0 ° C. and polymerized for 3 hours while maintaining this temperature. After completion of the polymerization, the reaction solution was heated to 100 ° C., 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour to obtain an alkali-soluble resin solution ( Solid content concentration = 33.2%) was obtained.
The obtained alkali-soluble resin had Mw = 8,500.
This alkali-soluble resin is referred to as “alkali-soluble resin (B-5)”.

Synthesis Example 6 (Production of alkali-soluble resin for comparison)
A flask equipped with a condenser and a stirrer was charged with 2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate, followed by 10 parts of methacrylic acid, 15 parts of styrene, and benzyl methacrylate. 30 parts, 25 parts of N-phenylmaleimide, 20 parts of ω-carboxypolycaprolactone mono (meth) acrylate, 2 parts of α-methylstyrene dimer as a chain transfer agent, purged with nitrogen, and then gently stirred to react. The solution was heated to 80 ° C. and polymerized for 3 hours while maintaining this temperature. After completion of the polymerization, the reaction solution was heated to 100 ° C., 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour to obtain an alkali-soluble resin solution ( Solid content concentration = 33.1%) was obtained.
The obtained alkali-soluble resin had Mw = 20,000.
This alkali-soluble resin is referred to as “alkali-soluble resin (B-6)”.

Synthesis Example 7 (Production of comparative alkali-soluble resin)
A flask equipped with a condenser and a stirrer was charged with 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate, followed by 10 parts of methacrylic acid, 15 parts of styrene, and benzyl methacrylate. 40 parts, 25 parts of N-phenylmaleimide, 10 parts of 2-hydroxyethyl methacrylate and 6.5 parts of α-methylstyrene dimer as a chain transfer agent were purged with nitrogen, and then gently stirred to prepare a reaction solution of 80 parts. The mixture was heated to 0 ° C. and polymerized for 3 hours while maintaining this temperature. After completion of the polymerization, the reaction solution was heated to 100 ° C., 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour to obtain an alkali-soluble resin solution ( Solid content concentration = 33.3%) was obtained.
The obtained alkali-soluble resin had Mw = 7,800.
This alkali-soluble resin is referred to as “alkali-soluble resin (B-7)”.

Example 6
<Preparation of liquid composition>
(A) 8 parts of a 80:20 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Red 177 as a colorant, 4 parts (in terms of solid content) of EFKA-47 as a dispersant, and propylene glycol monomethyl ether acetate as a solvent 75 parts were treated with a bead mill to prepare a pigment dispersion (R 6 ).
Subsequently, 87 parts of the obtained pigment dispersion (R 6 ), (B) 8 parts of an alkali-soluble resin (B −2 ) as an alkali-soluble resin, and (C) 2 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer And 4 parts of pentaerythritol tetraacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} as a photoradical generator -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 3 parts, 70 parts of 3-methoxybutyl acetate as a solvent and 96 parts of ethyl 3-ethoxypropionate were mixed to obtain a liquid composition (R 6 ). Prepared.

<Formation of colored layer>
The liquid composition (R 6 ) was applied to a soda glass substrate having a silicon dioxide (SiO ₂ ) film formed on its surface to prevent elution of sodium ions using a spin coater, and then on a hot plate at 90 ° C. Pre-baking was performed for 2 minutes to form a coating film having a thickness of 1.2 μm.
Next, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask (slit width 30 μm) using a high-pressure mercury lamp. The exposure amount at this time was 100 J / m ² . Thereafter, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 45 seconds, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to form a red stripe pixel pattern on the substrate.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 8 μm could be formed.
The main contents are shown in Table 2-1.

Example 7-20
<Preparation of liquid composition and formation of colored layer>
Pigment dispersions (R 7 ) to (R20) were prepared in the same manner as in Example 6 except that the dispersant was as shown in Table 2-1 or Table 2-2. Liquid compositions (R 7 ) to (R20) were prepared in the same manner as in Example 6 except that the resins were as shown in Table 2-1 or Table 2-2.
Next, a red stripe pixel pattern is formed on the substrate in the same manner as in Example 6 except that the liquid compositions (R 7 ) to (R 20) are used in place of the liquid composition (R 6 ). did.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 5, 6 to 8 μm could be formed. The main contents are shown in Table 2-1 and Table 2-2.

Example 2 6
<Preparation of liquid composition>
(A) 11 parts of a 60:40 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as the colorant, 4 parts of EFKA-47 as the dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate as the solvent 75 parts were treated with a bead mill to prepare a pigment dispersion (G 6 ).
Subsequently, 90 parts of the obtained pigment dispersion (G 6 ), (B) 8 parts of an alkali-soluble resin (B −2 ) as an alkali-soluble resin, and (C) 2 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer And 4 parts of pentaerythritol tetraacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} as a photoradical generator -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 3 parts, 70 parts of 3-methoxybutyl acetate as a solvent and 96 parts of ethyl 3-ethoxypropionate were mixed to obtain a liquid composition (G 6 ). Prepared. <Formation of colored layer>
Next, a green striped pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (G 6 ) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
When the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 8 μm could be formed.
The main contents are shown in Table 3-1.

Example 2 7-40
<Preparation of liquid composition and formation of colored layer>
Pigment dispersions (G 7 ) to (G 20) were prepared in the same manner as in Example 26 except that the dispersant was as shown in Table 3-1 or Table 3-2. Liquid compositions (G 7 ) to (G 20) were prepared in the same manner as in Example 26 except that the soluble resin was as shown in Table 3-1 or Table 3-2.
Next, a green striped pixel pattern is formed on the substrate in the same manner as in Example 6 except that the liquid compositions (G 7 ) to (G 20) are used in place of the liquid composition (R 6 ). did.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 5, 6 to 8 μm could be formed. The main contents are shown in Tables 3-1 and 3-2.

Example 4 6
<Preparation of liquid composition>
(A) 9 parts of a 95: 5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, 4 parts (in terms of solid content) of EFKA-47 as a dispersant, and propylene glycol monomethyl as a solvent 75 parts of ether acetate was treated with a bead mill to prepare a pigment dispersion (B 6 ).
Next, 88 parts of the obtained pigment dispersion (B 6 ), (B) 8 parts of an alkali-soluble resin (B −2 ) as an alkali-soluble resin, and (C) 2 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer And 4 parts of pentaerythritol tetraacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} as a photoradical generator -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 3 parts, 70 parts of 3-methoxybutyl acetate as a solvent and 96 parts of ethyl 3-ethoxypropionate were mixed to obtain a liquid composition (B 6 ). Prepared. <Formation of colored layer>
Next, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (B 6 ) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 8 μm could be formed.
The main contents are shown in Table 4-1.

Example 4 7-60
<Preparation of liquid composition and formation of colored layer>
Except that the dispersant was changed as shown in Table 4-1 or Table 4-2, in the same manner as in Example 4 6, after each pigment dispersion (B 7) ~ (B20) was prepared, (B) an alkali except that the soluble resin was as shown in Table 4-1 or Table 4-2, in the same manner as in example 4 6, respectively liquid composition (B 7) ~ (B20) was prepared.
Next, a blue stripe pixel pattern is formed on the substrate in the same manner as in Example 6 except that the liquid compositions (B 7 ) to (B 20) are used instead of the liquid composition (R 6 ). did.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 5, 6 to 8 μm could be formed. The main contents are shown in Tables 4-1 and 4-2.

Example 6 6
<Preparation of liquid composition>
(A) 20 parts of carbon black as a colorant, 4 parts of EFKA-46 as a dispersant (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to obtain a pigment dispersion (BK 6 ). Was prepared.
Subsequently, 99 parts of the obtained pigment dispersion (BK 6 ), (B) 8 parts of an alkali-soluble resin (B −2 ) as an alkali-soluble resin, and (C) 2 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer And 4 parts of pentaerythritol tetraacrylate, (D) Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} as a photoradical generator -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 3 parts and 150 parts of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (BK 6 ).
<Formation of colored layer>
Next, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (BK 6 ) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
When the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 6 μm could be formed.
The main contents are shown in Table 5-1.

Example 6 7-80
<Preparation of liquid composition and formation of colored layer>
Except that the dispersant was changed as shown in Table 5-1 or Table 5-2, in the same manner as in Example 6 6, after each pigment dispersion (BK 7) ~ (BK20) was prepared, (B) an alkali except that the soluble resin was as shown in Table 5-1 or Table 5-2, in the same manner as in example 6 6, respectively liquid composition (BK 7) ~ (BK20) was prepared.
Next, a black stripe pixel pattern is formed on the substrate in the same manner as in Example 6 except that the liquid compositions (BK 7 ) to (BK 20) are used in place of the liquid composition (R 6 ). did.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 5, 6 to 8 μm could be formed. The main contents are shown in Tables 5-1 and 5-2.

Comparative Example 1
<Preparation of liquid composition and formation of colored layer>
After preparing the pigment dispersion (R 6 ) in the same manner as in Example 6 , instead of 8 parts of the alkali-soluble resin (B -2 ), 2 parts of the alkali-soluble resin (B-5) and the alkali-soluble resin (B-) 6) A liquid composition (CR1) was prepared in the same manner as in Example 6 except that a mixture of 3 parts and 4 parts of the alkali-soluble resin (B-7) was used.
Next, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (CR1) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed and only a pattern with a line width of 40 μm could be formed.
The main contents are shown in Table 6.

Comparative Example 2
<Preparation of liquid composition and formation of colored layer>
Example 2 After preparing a pigment dispersion (G 7 ) in the same manner as in Example 7 , instead of 8 parts of the alkali-soluble resin (B -2 ), 2 parts of the alkali-soluble resin (B-5) and the alkali-soluble resin (B -6) A liquid composition (CG1) was prepared in the same manner as in Example 26 except that a mixture of 3 parts and 4 parts of the alkali-soluble resin (B-7) was used.
Next, a green stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (CG1) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, but when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), the undercut And only a pattern with a line width of 50 μm was formed. The main contents are shown in Table 6.

Comparative Example 3
<Preparation of liquid composition and formation of colored layer>
Example 4 After preparing a pigment dispersion (B 8 ) in the same manner as in Example 8 , instead of 8 parts of the alkali-soluble resin (B -2 ), 2 parts of the alkali-soluble resin (B-5) and the alkali-soluble resin (B -6) 3 parts of an alkali-soluble resin (B-7) except that a mixture of 4 parts, the same procedure as in example 4 6, liquid composition (CB1) was prepared.
Next, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (CB1) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, but when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed. And only a pattern with a line width of 45 μm could be formed. The main contents are shown in Table 6.

Comparative Example 4
<Preparation of liquid composition and formation of colored layer>
After preparing a pigment dispersion liquid (BK 9) in the same manner as in Example 6 9, the alkali-soluble resin (B -2) in place of 8 parts of an alkali-soluble resin (B-5) 2 parts of an alkali-soluble resin (B -6) 3 parts of an alkali-soluble resin (B-7) except that a mixture of 4 parts, the same procedure as in example 6 6, liquid composition (CBK1) was prepared.
Next, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (CBK1) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed and only a pattern with a line width of 40 μm could be formed.
The main contents are shown in Table 6.

Comparative Example 5
<Preparation of liquid composition and formation of colored layer>
After preparing a pigment dispersion (R 10 ) in the same manner as in Example 10 , instead of 8 parts of the alkali-soluble resin (B -2 ), 2 parts of the alkali-soluble resin (B-5) and the alkali-soluble resin (B- 6) A liquid composition (CR2) was prepared in the same manner as in Example 6 except that a mixture of 3 parts and 4 parts of the alkali-soluble resin (B-7) was used.
Next, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 6 except that the liquid composition (CR2) was used instead of the liquid composition (R 6 ).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed and only a pattern with a line width of 45 μm could be formed.
The main contents are shown in Table 6.

Claims (5)

A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photoradical generator, wherein (B) the alkali-soluble resin The aromatic ring in the main chain has an aromatic hydrocarbon skeleton selected from the group of naphthalene ring, 2,2′-binaphthyl ring, biphenylene ring, acenaphthylene ring, acenaphthene ring, phenanthrene ring, anthracene ring or perylene ring , And the radiation sensitive composition for colored layer formation characterized by including polyester which has a polymerizable unsaturated bond in a side chain. (B) The polyester having an aromatic hydrocarbon skeleton in the main chain constituting the component and having a polymerizable unsaturated bond in the side chain is a polyester represented by the following formula (1): The radiation sensitive composition for colored layer formation of Claim 1.

[In the formula (1), each X independently represents a divalent group represented by the following formula (3), formula (4) or formula (5), and each Y independently represents a carboxyl group. 4 represents a residue excluding a carboxyl group of an organic compound having four, each R ¹ independently represents a hydrogen atom or a methyl group, and each R ² independently represents a hydrogen atom or a carboxyl group blocking agent residue. N is an integer of 1-40. However, the two bonds marked with * in the formula are directly connected to each other.

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and p is 0 -4 is an integer, and q is an integer of 0-4.)

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and p is 0 -4 is an integer, and q is an integer of 0-4.)

(However, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ³ and R ⁴ may be the same or different from each other, and r is 0 ) Is an integer of -6, and s is an integer of 0-6.)] (D) The radiation sensitive material for forming a colored layer according to claim 1, wherein the photoradical generator contains a compound represented by the following formula (6) or formula (7) as an essential component. Sex composition.

[In the formula (6), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). Show
R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ are present. R ⁹ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a carbon atom having 4 to 20 carbon atoms. A monovalent sulfur-containing heterocyclic group, and a plurality of R ⁹ may be the same or different from each other, a is an integer of 0 to 5, b is an integer of 0 to 5, and (a + b) ≦ 5 is there. ]

[In Formula (7), R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, carbon number 1 -20 alkyl group, cycloalkyl group having 3 to 8 carbon atoms, phenyl group which may be substituted, or monovalent alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group). Show
R ⁸ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or a cycloalkyloxy group having 3 to 8 carbon atoms, and a plurality of R ⁸ are present. R ⁹ may be the same as or different from each other, and R ⁹ is a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a carbon atom having 4 to 20 carbon atoms. A monovalent sulfur-containing heterocyclic group, and a plurality of R ⁹ may be the same or different from each other, c is an integer of 0 to 5, d is an integer of 1 to 5, and (c + d) ≦ 5 Yes, e is an integer of 0-6. ]   The color filter which has a colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-3.   A color liquid crystal display device comprising the color filter according to claim 4.