JP4706559B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

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. The present invention relates to a radiation-sensitive composition used for forming a useful colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display element 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 required performance for formed pixels, black matrices and colored radiation-sensitive compositions has become increasingly severe. For pixels and black matrices, solvent resistance and substrates for a wide range of solvents are required. In terms of production control of color filters, the colored radiation-sensitive composition used for forming color filters is stable as a liquid composition containing a solvent. Although the point which is excellent in property is also calculated | required strongly, the conventional coloring radiation sensitive composition was not able to fully satisfy | fill these requirements.

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

  An object of the present invention is to provide a novel coloring that gives a pixel and a black matrix that have good storage stability as a liquid composition containing a solvent, and also have excellent solvent resistance to a wide range of solvents, adhesion to a substrate, etc. The object is to provide a radiation-sensitive composition for layer formation.

The present invention, first,
In the radiation-sensitive composition for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, (B) alkali-soluble The resin is at least one selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound, and (b2) tetrahydrofuran ester of (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate , 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (meth) acryloyloxypropionic acid Of tetrahydrofurfuryl group-containing esters having a tetrahydrofuran skeleton A copolymer comprising at least one unsaturated compound having a tetrahydrofuran skeleton selected from the group of nylbenzene derivatives and vinyl ethers having a tetrahydrofuran skeleton, and (b3) an unsaturated compound having an oxetane skeleton as essential constituents A radiation-sensitive composition for forming a colored layer.
In the present invention, the colored layer means “pixel and / or black matrix”.

The present invention secondly,
It comprises a color filter comprising a colored layer formed through the step of irradiating a coating film of the colored layer forming radiation-sensitive composition with the radiation-sensitive composition for forming the colored layer.

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- (A) Colorant-
The colorant in the present invention is not particularly limited in color tone, 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 compounds classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (C .. I.) Numbers can be mentioned.

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

C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

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

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

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60;
C. I. Pigment green 7, C.I. I. Pigment green 36;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.
These organic pigments 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 (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 organic pigment and the inorganic pigment can be used alone or in admixture of two or more, and the organic pigment and the inorganic pigment can be used in combination. Preferably, one or more organic pigments are used, and two or more organic pigments and / or carbon black are preferably used in forming the black matrix.

  In the present invention, each of the pigments 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 & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), BYK, Disperbyk (Bicchemy Japan) Product), Solsperse (manufactured by Seneca Corporation), 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, for example, by mixing the components (A) to (D) together with a solvent or an additive described later in some cases. However, when a pigment is used as a colorant, the pigment is mixed in a solvent in the presence of a dispersant, optionally together with a part of the component (B), for example, using a bead mill, a roll mill or the like. It is preferable to prepare a pigment dispersion by dispersing and adding the components (B) to (D) and, if necessary, additional solvents and additives, and mixing them.

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 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 500 to 1,000 parts by weight, preferably 700 to 900 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 mixture 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) Alkali-soluble resin-
The alkali-soluble resin in the present invention is at least one selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound (hereinafter these compounds are collectively referred to as “acidic unsaturated compound”). (B2) (meth) acrylic acid tetrahydrofuran esters, tetrahydrofurfuryl (meth) acrylate, 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl (meth) acrylate, tetrahydrofurfuryl group-containing esters of 2- (meth) acryloyloxypropionic acid, vinylbenzene derivatives having a tetrahydrofuran skeleton, and vinyl ether having a tetrahydrofuran skeleton An unsaturated compound having at least one tetrahydrofuran skeleton selected from the group of ethers (hereinafter referred to as “tetrahydrofuran-based unsaturated compound”) and (b3) an unsaturated compound having an oxetane skeleton (hereinafter referred to as “oxetane-based unsaturated compound”). (Hereinafter referred to as “copolymer (BI)”), (A) acts as a binder for the colorant, and is a colored layer. Is a component that is soluble in an alkaline developer used in the development processing step when forming the.

Examples of the unsaturated carboxylic acid or acid anhydride thereof 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 carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Of these unsaturated carboxylic acids or acid anhydrides thereof, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively light ester HOA-MS and light ester HOA-MPE ( As mentioned above, it is marketed under the trade name of Kyoeisha Chemical Co., Ltd.

Examples of the unsaturated phenol compound include:
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols.

  In the present invention, (meth) acrylic acid, p-vinylphenol and the like are preferable as the acidic unsaturated compound, and (meth) acrylic acid is particularly preferable.

Other than tetrahydrofurfuryl (meth) acrylate, 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate and 2- (3-tetrahydrofurfuryloxy) ethyl (meth) acrylate Examples of the tetrahydrofuran-based unsaturated compound include:
Tetrahydrofuran esters of (meth) acrylic acid such as tetrahydrofuran-2-yl (meth) acrylate and tetrahydrofuran-3-yl (meth) acrylate;
2- (meth) acryloyloxypropionic acid tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 3-tetrahydrofurfuryl, 2- (meth) acryloyloxypropionic acid 2- (tetrahydrofurfuryloxy) ethyl, 2- ( Tetrahydrofurfuryl group-containing esters of 2- (meth) acryloyloxypropionic acid such as 2- (3-tetrahydrofurfuryloxy) ethyl such as (meth) acryloyloxypropionic acid,

Vinylbenzene derivatives such as (tetrahydrofuran-2-yl) oxy-p-vinylbenzene, (tetrahydrofurfuryl) oxy-p-vinylbenzene, 2- (tetrahydrofurfuryloxy) ethoxy-p-vinylbenzene;
Examples thereof include vinyl ethers such as (tetrahydrofuran-2-yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, and [2- (tetrahydrofurfuryloxy) ethyl] vinyl ether.

In the present invention, tetrahydrofurfuryl (meth) acrylate is particularly preferable as the tetrahydrofuran unsaturated compound.
The said tetrahydrofuran type unsaturated compound can be used individually or in mixture of 2 or more types.

  Moreover, as an oxetane type unsaturated compound, Preferably, for example, a compound represented by the following general formula (1) (hereinafter referred to as “oxetane type unsaturated compound (1)”), the following general formula (2): And the like (hereinafter referred to as “oxetane-based unsaturated compound (2)”).

[In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of one another, R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms. , N is an integer of 0-6. ]

In [Formula ^{(2), R, R 1} , R 2, R 3, R 4, R 5 and n are each in the general formula ^{(1) R, R 1,} R 2, R 3, R 4, R Synonymous with ⁵ and n. ]

In general formula (1) and general formula (2), examples of the alkyl group having 1 to 4 carbon atoms of R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ include, for example, a methyl group, an ethyl group, n- A propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like can be mentioned.
Examples of the fluoroalkyl group having 1 to 4 carbon atoms of R ² , R ³ , R ⁴ and R ⁵ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, and 2-fluoro Ethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, Nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group and the like can be mentioned.
As the R ^2, R ^3, aryl group having 6 to 20 carbon atoms of R ⁴ and R ^5, for example, a phenyl group, o- tolyl group, m- tolyl group, a p- tolyl .

As the oxetane unsaturated compound (1), for example,
3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -2-methyloxetane, 3-[(meth) acryloyloxymethyl] -3-methyloxetane, 3-[(meth) Acryloyloxymethyl] -2-ethyloxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) [Acryloyloxymethyl] -2-pentafluoroethyloxetane, 3-[(meth) acryloyloxymethyl] -2-phenyloxetane, 3-[(meth) acryloyloxymethyl] -2,2-difluorooxetane, 3-[( (Meth) acryloyloxymethyl] -2,2,4-trifluoro Kisetan, 3 - [(meth) acryloyloxy methyl] -2,2,4,4-tetrafluorooxetane,

3- [2- (meth) acryloyloxyethyl] oxetane, 3- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 3- [2- (meth) acryloyloxyethyl] -3-methyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -3-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2 -Trifluoromethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-phenyloxetane, 3- [2- ( (Meth) acryloyloxyethyl] -2,2-difluorooxetane, 3- [2- (meth) acryloyl (Meth) acrylic acid esters such as xylethyl] -2,2,4-trifluorooxetane and 3- [2- (meth) acryloyloxyethyl] -2,2,4,4-tetrafluorooxetane Can do.

Moreover, as an oxetane type unsaturated compound (2), for example,
2-[(meth) acryloyloxymethyl] oxetane, 2-[(meth) acryloyloxymethyl] -2-methyloxetane, 2-[(meth) acryloyloxymethyl] -3-methyloxetane, 2-[(meth) Acryloyloxymethyl] -4-methyloxetane, 2-[(meth) acryloyloxymethyl] -2-ethyloxetane, 2-[(meth) acryloyloxymethyl] -3-ethyloxetane, 2-[(meth) acryloyloxy Methyl] -4-ethyloxetane, 2-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 2-[(meth) acryloyloxymethyl] -3-trifluoromethyloxetane, 2-[(meth) [Acryloyloxymethyl] -4-trifluoromethyloxetane, 2 [(Meth) acryloyloxymethyl] -2-pentafluoroethyloxetane, 2-[(meth) acryloyloxymethyl] -3-pentafluoroethyloxetane, 2-[(meth) acryloyloxymethyl] -4-pentafluoroethyl Oxetane,

2-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] -3-phenyloxetane, 2-[(meth) acryloyloxymethyl] -4-phenyloxetane, 2- [(Meth) acryloyloxymethyl] -2,3-difluorooxetane, 2-[(meth) acryloyloxymethyl] -2,4-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3,3-difluoro Oxetane, 2-[(meth) acryloyloxymethyl] -3,4-difluorooxetane, 2-[(meth) acryloyloxymethyl] -4,4-difluorooxetane, 2-[(meth) acryloyloxymethyl] -3 , 3,4-trifluorooxetane, 2-[(meth) acryloyloxy Methyl] 3,4,4-trifluoro oxetane, 2 - [(meth) acryloyloxy methyl] 3,3,4,4 tetrafluorooxetane

2- [2- (meth) acryloyloxyethyl] oxetane, 2- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-methyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -3 -Ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-trifluoromethyloxetane, 2- [2- (meth) [Acryloyloxyethyl] -3-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -4-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-pentafluoroethyloxetane, 2 -[2- (meth) acryloyloxyethyl] -4-pentafluoroethyloxetane,

2- [2- (meth) acryloyloxyethyl] -2-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -3-phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -4 -Phenyloxetane, 2- [2- (meth) acryloyloxyethyl] -2,3-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -2,4-difluorooxetane, 2- [2- ( (Meth) acryloyloxyethyl] -3,3-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -4,4 -Difluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,3,4-trifluorooxe 2- [2- (meth) acryloyloxyethyl] -3,4,4-trifluorooxetane, 2- [2- (meth) acryloyloxyethyl] -3,3,4,4-tetrafluorooxetane, etc. (Meth) acrylic acid esters and the like.

  Of these oxetane unsaturated compounds (1) and oxetane unsaturated compounds (2), 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] oxetane, 2-[( (Meth) acryloyloxymethyl] -4-trifluoromethyloxetane and the like are preferable, and in particular, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2 -Trifluoromethyloxetane, 3- ( Tacriroyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. have a wide development margin for the resulting radiation-sensitive composition, And from the point which improves the chemical resistance of the colored layer obtained.

In the present invention, as the oxetane unsaturated compound, in addition to the oxetane unsaturated compound (1) and the oxetane unsaturated compound (2), for example,
(3-oxetanylmethoxy) -p-vinylbenzene, [2- (3-oxetanyl) ethoxy] -p-vinylbenzene, (2-oxetanylmethoxy) -p-vinylbenzene, [2- (2-oxetanyl) ethoxy] -(Oxetanylalkyl) ethers of vinylphenols such as p-vinylbenzene;
Use of (oxetanylalkyl) vinyl ethers such as (3-oxetanylmethyl) vinyl ether, [2- (3-oxetanyl) ethyl] vinyl ether, (2-oxetanylmethyl) vinyl ether, [2- (2-oxetanyl) ethyl] vinyl ether, etc. You can also
The oxetane unsaturated compounds can be used alone or in admixture of two or more.

In some cases, the copolymer (BI) contains, as a constituent component, an unsaturated compound other than an acidic unsaturated compound, a tetrahydrofuran unsaturated compound, and an oxetane unsaturated compound (hereinafter referred to as “other unsaturated compound”). Furthermore, it can contain.
Examples of other unsaturated compounds include:
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;
Unsaturated imides such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and itaconimide;

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 (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
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;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include 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, and polysiloxane.
These other unsaturated compounds can be used alone or in admixture of two or more.

In the present invention, the copolymer (B1) includes (b1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component and (b2) a tetrahydrofuran-based unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component. Saturated compounds and (b3) 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) ) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and at least one oxetane unsaturated compound selected from the group of 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane (B4) Len, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer A copolymer further containing at least one other unsaturated compound selected from the group (hereinafter referred to as “copolymer (BII)”) is preferred.

As the copolymer (BII), more specifically, for example,
(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 3-[(meth) (Acryloyloxymethyl) oxetane-based unsaturated compound containing oxetane as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Copolymer containing at least one other unsaturated compound selected from the group of allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer (BII -1);
(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 3-[(meth) Acryloyloxymethyl] -3-ethyloxetane as an essential component and an oxetane unsaturated compound as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl ( A copolymer containing at least one other unsaturated compound selected from the group of (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethylmethacrylate macromonomer. Polymer (BII-2);

(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 3-[(meth) Acryloyloxymethyl] -2-trifluoromethyloxetane as an essential component and an oxetane unsaturated compound as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxy Contains at least one other unsaturated compound selected from the group of ethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer Copolymer ( II-3);
(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 3-[(meth) An oxetane-based unsaturated compound containing acryloyloxymethyl] -2-phenyloxetane as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl ( A copolymer containing at least one other unsaturated compound selected from the group of (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethylmethacrylate macromonomer. Polymer (BII-4);

(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 2-[(meth) (Acryloyloxymethyl) oxetane-based unsaturated compound containing oxetane as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Copolymer (BII) containing at least one other unsaturated compound selected from the group of allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer -Five) ;
(B1) an acidic unsaturated compound containing (meth) acrylic acid as an essential component, (b2) a tetrahydrofuran unsaturated compound containing tetrahydrofurfuryl (meth) acrylate as an essential component, and (b3) 2-[(meth) (Acryloyloxymethyl) -4-trifluoromethyloxetane as an essential component and an oxetane unsaturated compound as an essential component, and in some cases (b4) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxy Contains at least one other unsaturated compound selected from the group of ethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer Copolymer ( II-6)
Etc.

  Of these copolymers (BII), the copolymer (BII-1) and the copolymer (BII-2) are particularly preferred.

In the copolymer (BI), the copolymerization ratio of the acidic unsaturated compound is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the tetrahydrofuran unsaturated compound is preferably 1 to 70% by weight, particularly preferably 1 to 40% by weight, and the copolymerization ratio of the oxetane-based unsaturated compound is preferably 1 to 60% by weight, particularly preferably 1 to 40% by weight. The copolymerization ratio of the saturated compound is usually 0 to 70% by weight, preferably 1 to 60% by weight.
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (BI) to the above range, the radiation sensitivity for forming a colored layer excellent in sensitivity, adhesion to a substrate, solvent resistance, and the like. A composition can be obtained.

In the present invention, other alkali-soluble resins can be used in combination with the copolymer (BI).
The other alkali-soluble resin is not particularly limited as long as it functions as a binder for (A) the colorant and is soluble in the alkali developer used in the development processing step when forming the colored layer. For example, an alkali-soluble resin having a carboxyl group (hereinafter referred to as “another carboxyl group-containing alkali-soluble resin”) is preferable.
As other carboxyl group-containing alkali-soluble resin, for example, at least one of the carboxyl group-containing unsaturated compounds exemplified for the copolymer (BI) and at least one of other unsaturated compounds exemplified for the copolymer (BI) From the group of tetrahydrofuran-type unsaturated compounds and other unsaturated compounds exemplified for the copolymer (BI) and at least one of the carboxyl group-containing unsaturated compounds exemplified for the copolymer (BI) and the copolymer (BI). Copolymer with at least one kind selected, oxetane unsaturated compound exemplified with respect to at least one carboxyl group-containing unsaturated compound exemplified for copolymer (BI) and copolymer (BI), and other unsaturated compounds Examples thereof include a copolymer with at least one selected from the group of compounds.

  More preferable examples of the other carboxyl group-containing alkali-soluble resin include (i) a carboxyl group-containing unsaturated compound containing (meth) acrylic acid as an essential component, and (ii) styrene, N-phenylmaleimide, methyl. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, tetrahydrofurfuryl (meth) acrylate 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3- [ ( T) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] oxetane and 2-[(meth) acryloyloxymethyl] -4-trifluoromethyloxetane; And the like.

In the present invention, the polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is as follows. Usually, it is 3,000 to 300,000, preferably 5,000 to 100,000.
The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is usually as follows. It is 3,000-60,000, preferably 5,000-25,000.
In the present invention, the copolymer (BI) having the specific Mw and Mn is used, or the copolymer (BI) and another alkali-soluble resin having the specific Mw and Mn are used in combination. Thus, a radiation-sensitive composition having excellent developability can be obtained, whereby a pixel having a sharp pattern edge and a black matrix can be formed, and on the unexposed portion of the substrate and on the light shielding layer during development Residues, dirt, film residue, etc. are less likely to occur.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the copolymer (BI) and other alkali-soluble resins is preferably 1 to 5, and more preferably 1 to 4, respectively.

In this invention, a copolymer (BI) can be used individually or in mixture of 2 or more types, and other alkali-soluble resin is also the same.
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 10 parts by weight, for example, the alkali developability may decrease, or there may be scumming or film residue on the unexposed part of the substrate or the light shielding layer On the other hand, when the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.
Moreover, the usage-amount of the copolymer (BI) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Most preferably, it is 30-100 weight%. In this case, if the proportion of the copolymer (BI) used is less than 10% by weight, the intended effect of the present invention may be impaired.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional 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 hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends 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,

Compound represented by the following formula (3)

And a compound represented by the following formula (4):

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate have a 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 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or 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 (B) compounds similar to those exemplified for the acidic unsaturated compound, N-substituted maleimide or other unsaturated compound in the alkali-soluble resin, and N- (meth). 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, when the use ratio of the monofunctional monomer exceeds 90% by weight, 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 5 parts by weight, the strength and surface smoothness of the colored layer tend to be lowered. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is lowered or unexposed parts There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization of the body.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. Examples include compounds, O-acyloxime compounds, onium salt compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.
In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, acetophenone compounds, biimidazole compounds, triazine compounds and At least one selected from the group of O-acyloxime compounds is preferred.

  In this invention, the general usage-amount of a photoinitiator is 0.01-120 weight normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer. Parts, preferably 1 to 100 parts by weight. In this case, when the amount of the photopolymerization initiator used is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 120 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 80 parts by weight, the formed colored layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 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'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .

  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, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′. -Biimidazole is preferred.

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which a colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, 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 the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below 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 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based 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 “ 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, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted 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.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a 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 thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

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 from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the 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, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 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.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 parts by weight, the effect of improving the sensitivity tends to decrease. On the other hand, if it exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the amount of triazine compound used as the photopolymerization initiator is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

  Specific examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio). Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole -3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetate) Ruokishimu), and the like.

Of these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime) and the like are preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using an O-acyloxime compound as a photopolymerization initiator is based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-40 weight part, More preferably, it is 1-30 weight part, Most preferably, it is 1-20 weight part. In this case, if the amount of the O-acyloxime compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Examples of the onium salt compounds include diaryliodonium salts, triarylsulfonium salts, diarylphosphonium salts, and the like.
Specific examples of the diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoro Acetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert- Examples thereof include butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, and bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate.

Specific examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenyl Sulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldipheny Sulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4 -Phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluenesulfonate and the like can be mentioned.
Specific examples of the diarylphosphonium salts include (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphonate.

  Of these onium salt compounds, diphenyliodonium hexafluorophosphonate, triphenylsulfonium trifluoromethanesulfonate, and the like are particularly preferable. The said onium salt type compound can be used individually or in mixture of 2 or more types.

  In the present invention, the amount used in the case of using an onium salt compound as a photopolymerization initiator is preferably (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the amount of the onium salt compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

-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 (excluding the hydrogen donor), a curing agent, a curing aid, and the like.

The organic acid and the organic amino compound are components that improve the solubility of the radiation-sensitive composition in an alkaline developer and further suppress the remaining undissolved material after development.
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.

Of these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, and prevention of background contamination and film residue on the substrate or the light shielding layer in the unexposed area. 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 entire solid content of the radiation-sensitive composition. In this case, when the usage-amount of organic acid exceeds 15 weight%, 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 said hardening | curing agent is a component which reacts with the carboxyl group and / or oxetane ring in (B) alkali-soluble resin, and hardens this (B) alkali-soluble resin.
Examples of such curing agents include epoxy compounds and oxetane compounds.
The epoxy compound is preferably a polyfunctional epoxy compound, and specific examples thereof include fragrances such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolak epoxy resin. Other epoxy resins such as alicyclic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, and the like, as well as brominated derivatives of these epoxy resins, butadiene (Co) polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl group-containing unsaturated compound (co) polymer, triglycidyl isocyanurate, and the like.

  Moreover, an epoxy group-containing unsaturated compound is also preferable as the epoxy compound, and specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, Examples include o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

The oxetane compound is preferably a polyfunctional oxetane compound. Specific examples thereof include bisoxetanyl carbonate, bisoxetanyl adipate, bisoxetanyl terephthalate, bisoxetanyl p-xylylene dicarboxylate, and 1,4-cyclohexanedicarboxylic acid. High molecular compounds such as low molecular weight compounds such as bisoxetanyl acid, oxetane etherified products of phenol novolac resins, and (co) polymers of unsaturated compounds having an oxetane ring structure (excluding copolymer (B1)). Can be mentioned. The copolymer (B1) has an oxetane ring structure and falls within the category of an oxetane compound as a curing agent.
A compound having both an oxetane ring structure and an unsaturated double bond is also preferred as the oxetane compound, and specific examples thereof include the oxetane unsaturated compounds.

These hardening | curing agents can be used individually or in mixture of 2 or more types.
The amount of the curing agent used is usually 30% by weight or less, preferably 20% by weight or less, based on the entire solid content of the radiation-sensitive composition. In this case, when the usage-amount of a hardening | curing agent exceeds 30 weight%, there exists a tendency for the storage stability of the obtained radiation sensitive composition to fall.

The curing aid is a component that accelerates the curing reaction by the curing agent by opening the epoxy group and / or oxetane ring of the curing agent.
Examples of such curing aids include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, amino compounds, thermal acid generators, and the like.

Specific examples of the polyvalent carboxylic acid include the same compounds as those having two or more carboxyl groups in the organic acid, and specific examples of the amino compound are the same as those of the organic amino compound. Can be mentioned.
Specific examples of the polyvalent carboxylic acid anhydride include aromatics such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Polycarboxylic acid anhydrides; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Aliphatic polycarboxylic anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid Anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, anhydrous hymic acid, no Alicyclic polycarboxylic anhydrides such as water nadic acid; ester group-containing carboxylic anhydrides such as ethylene glycol bistrimellitic anhydride and glycerin tristrimellitic anhydride, Adeka Hardener EH-700 ( Asahi Denka Kogyo Co., Ltd.), Rikacid HH (Shin Nippon Rika Co., Ltd.), MH-700 (Shin Nihon Rika Co., Ltd.), etc. Can do.

  Examples of the thermal acid generator include sulfonium salts (excluding the triarylsulfonium salts mentioned for the photopolymerization initiator (D)), benzothiazonium salts, ammonium salts, phosphonium salts, sulfones. An acid ester compound, a sulfonimide compound, a diazomethane compound and the like can be mentioned, and among these, sulfonium salts, benzothiazonium salts, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds and the like are preferable.

Specific examples of the sulfonium salts include
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexa Alkylsulfonium salts such as fluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salt;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Examples thereof include substituted benzylsulfonium salts such as hexafluoroantimonate.

  Specific examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- Benzylbenzo such as (p-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Examples include thiazonium salts.

  Specific examples of the sulfonate compound include benzoin tosylate, α-methylol benzoin tosylate, α-methylol benzoin n-octane sulfonate, pyrogallol tris (trifluoromethane sulfonate), pyrogallol tris (nonafluoro-n-butane sulfonate). ), Pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy. Imido, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-[(5- And methyl-5-carboxymethanebicyclo [2.2.1] hept-2-yl) sulfonyloxy] succinimide.

  Specific examples of the diazomethane compound include bis (cyclohexanesulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (1,4-dioxaspiro [4.5] -decan-7-sulfonyl) diazomethane. be able to.

  Among these thermal acid generators, in particular, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4- Hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -En-2,3-dicarboximide and the like are preferable.

The said hardening adjuvant can be used individually or in mixture of 2 or more types.
The amount of the curing aid used is usually 15% by weight or less, preferably 10% by weight or less, based on the entire solid content of the radiation-sensitive composition. In this case, when the amount of the curing aid used exceeds 15% by weight, the storage stability of the resulting radiation-sensitive composition tends to decrease, or the formed colored layer tends to fall off from the substrate during development. .

Furthermore, as an additive other than the above, 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-methacryloyloxypropyltrimethoxysilane, 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 comprises 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;

(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl 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-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, 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, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
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, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl Rubin acid 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 composition is usually from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

Color filter The color filter of the present invention comprises a colored layer formed using the radiation-sensitive composition for forming a colored layer of the present 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 product, pre-baking is performed to evaporate the solvent, thereby forming 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 the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, 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 is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
Further, the black matrix can be formed in the same manner as in the case of forming the pixel by using a liquid composition of a radiation sensitive composition in which a black pigment is dispersed, for example.

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. (E)
(A) (B) A radiation-sensitive composition for forming a colored layer, wherein the alkali-soluble resin contains a copolymer (BII).
(B) The radiation-sensitive composition for forming a colored layer according to (i), wherein the copolymer (BII) contains at least one selected from the group of copolymers (BII-1) to (BII-6).
(C) (C) The colored layer of (A) or (B), wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation sensitive composition for forming.
(D) The radiation sensitivity for forming a colored layer of the above (a), (b) or (c), wherein the photopolymerization initiator is at least one selected from the group of acetophenone compounds, biimidazole compounds and triazine compounds. Composition. (E) (A) The radiation-sensitive composition for forming a colored layer according to (a), (b), (c) or (d), wherein the colorant comprises an organic pigment or carbon black.

Further, the preferred color filter of the present invention is
(F) Using the radiation-sensitive composition for forming a colored layer according to (i), (b), (c), (d) or (e), the coating film of the radiation-sensitive composition for forming a colored layer The pixel and / or black matrix formed through the process of irradiating with radiation is provided.

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

The radiation-sensitive composition for forming a colored layer of the present invention has a pixel pattern having excellent storage stability as a liquid composition, excellent solvent resistance against a wide range of solvents, adhesion to a substrate, and the like. A black matrix pattern can be formed.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be very suitably used 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.
Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts of 2,2′-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate, followed by 15 parts of methacrylic acid, 15 parts of tetrahydrofurfuryl methacrylate, 3- ( Methacryloyloxymethyl) -3-ethyloxetane (15 parts), benzyl methacrylate (55 parts), and 3 parts of α-methylstyrene dimer as a molecular weight regulator were charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution. This resin is referred to as “alkali-soluble resin (B-1)”.

Synthesis Examples 2-8 and Comparative Synthesis Examples 1-6
Except having changed the unsaturated compound which comprises alkali-soluble resin into the kind and quantity shown in Table 1, it carried out similarly to the synthesis example 1, and obtained each solution of alkali-soluble resin (B-2)-(B-14). .

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 80/20 (weight ratio) 20 parts of a mixture, 5 parts of BYK-2001 as a dispersant (in terms of solid content), 75 parts of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill, and pigment dispersion (R) was prepared.

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 50/50 (weight ratio) mixture, 5 parts of Solsperse 24000 as a dispersant (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to obtain a pigment dispersion ( G) was prepared.

Example 1
100 parts of pigment dispersion (R), 15 parts of the alkali-soluble resin (B-1) as the resin solution obtained in Synthesis Example 1 (in terms of solid content), (C) dipentaerythritol hexaacrylate as the polyfunctional monomer 10 parts and 5 parts trimellilol propane triacrylate, (D) 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 4, 4 ′ -3 parts of bis (diethylamino) benzophenone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R-1) having a solid concentration of 25%.

The liquid composition (R-1) was evaluated by forming a pattern according to the following procedure. The evaluation results are shown in Table 6.
Pattern formation The liquid composition (R-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. . Thereafter, the three substrates were cooled to room temperature, and the coating film on each substrate was exposed to the coating film on each substrate through a photomask at an exposure amount of 2000 J / m ² using a high pressure mercury lamp. Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. was discharged onto the coating film on each substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development, and then at 220 ° C. Post baking was performed for 30 minutes to form a 200 × 200 μm dot pattern.

Evaluation of solvent resistance Three substrates exposed at an exposure dose of 2000 J / m ² were N-methylpyrrolidone (referred to as “NMP” in Table 6 and Table 7) at 25 ° C., 18% HCl aqueous solution (Table 6 and Table 6). 7 is referred to as “HCl”) or 5% KOH aqueous solution (referred to as “KOH” in Tables 6 and 7) for 30 minutes, and the dot pattern before and after immersion is observed with a scanning electron microscope. When the pattern is well formed and the film thickness ratio before and after immersion (film thickness after immersion x 100 / film thickness before immersion) is 95% or more, the film thickness ratio before and after immersion is less than 95%. Or a case where a part of the pattern was found to be chipped was evaluated as Δ, and a case where the pattern was all peeled off from the substrate after immersion was evaluated as ×.

Adhesion evaluation The liquid composition (R-1) was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C. for 4 minutes to form a coating film having a thickness of 1.3 μm. . Then, after cooling this board | substrate to room temperature, the coating film was exposed by the exposure amount of 2000 J / m < ² > using the high pressure mercury lamp. Thereafter, a 0.04% aqueous potassium hydroxide solution at 23 ° C. was discharged onto the coating film at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) to perform shower development, followed by post-baking at 220 ° C. for 30 minutes. It was. Then, according to the JIS K5400 standard, the coating film is cross-cut into 100 grids, and an adhesion test is performed. If the grids are not peeled off, 1 or 10 of the grids are peeled off. The case was evaluated as Δ and the case where more than 10 grids were peeled off was evaluated as ×.

Storage stability evaluation of the liquid composition When the liquid composition (R-1) is placed in a glass bottle and stored in a constant temperature and humidity chamber at 40 ° C for one week, the viscosity before and after storage is measured and the rate of change in viscosity is measured. (Viscosity after storage × 100 / viscosity before storage) was calculated. The viscosity of the pigment dispersion (R) and the solution viscosity of the alkali-soluble resin (B-1) used here were not changed even when stored under the same conditions as described above.

Examples 2-12
Liquid compositions (R-2) to (R-12) were prepared in the same manner as in Example 1, except that the components in Example 1 were changed as shown in Table 2.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (R-2) to (R-12) were used in place of the liquid composition (R-1). In addition, even if each solution viscosity of alkali-soluble resin (B-2)-(B-8) used in Examples 6-12 was preserve | saved on the conditions similar to the case in the storage stability evaluation of the said liquid composition. No change was observed. The evaluation results are shown in Table 6.

Example 13
100 parts of pigment dispersion (G), 15 parts of the alkali-soluble resin (B-1) as the resin solution obtained in Synthesis Example 1 (in terms of solid content), (C) dipentaerythritol hexaacrylate as the polyfunctional monomer 5 parts and 10 parts of pentaerythritol tetraacrylate, (D) 5 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 5 parts of diethylthioxanthone as a photopolymerization initiator, Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a liquid composition (G-1) having a solid concentration of 25%.
Subsequently, a pattern was formed and evaluated in the same manner as in Example 1 except that the liquid composition (G-1) was used in place of the liquid composition (R-1). The viscosity of the pigment dispersion (G) used here did not change even when stored under the same conditions as in the storage stability evaluation of the liquid composition. The evaluation results are shown in Table 6.

Examples 14-24
In Example 13, liquid compositions (G-2) to (G-12) were prepared in the same manner as in Example 13, except that the components were changed as shown in Table 3.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G-2) to (G-12) were used in place of the liquid composition (R-1). The evaluation results are shown in Table 6.

Comparative Examples 1-10
In Example 1, liquid compositions (R-13) to (R-22) were prepared in the same manner as in Example 1 except that the constituent components were changed as shown in Table 4.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (R-13) to (R-22) were used in place of the liquid composition (R-1). Table 7 shows the evaluation results.

Comparative Examples 11-20
In Example 13, liquid compositions (G-13) to (G-22) were prepared in the same manner as in Example 13 except that the constituent components were changed as shown in Table 5.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G-13) to (G-22) were used in place of the liquid composition (R-1). Table 7 shows the evaluation results.

In Tables 2-5, the content of a polyfunctional monomer, a photoinitiator, and an additive is as follows.
Multifunctional monomer C-1: Dipentaerythritol hexaacrylate C-2: Trimethylolpropane triacrylate C-3: Pentaerythritol tetraacrylate
Photopolymerization initiator D-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one D-2: 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one D-3: 4,4′-bis (diethylamino) benzophenone D-4: 2,4-diethylthioxanthone
Additive E-1: Bisphenol A novolak epoxy resin (trade name 157S65, manufactured by Japan Epoxy Resin Co., Ltd.)
E-2: trimellitic anhydride E-3: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide

Claims (3)

In the radiation-sensitive composition for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, (B) alkali-soluble The resin is at least one selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound, and (b2) tetrahydrofuran ester of (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate , 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (meth) acryloyloxypropionic acid Of tetrahydrofurfuryl group-containing esters having a tetrahydrofuran skeleton A copolymer comprising at least one unsaturated compound having a tetrahydrofuran skeleton selected from the group of nylbenzene derivatives and vinyl ethers having a tetrahydrofuran skeleton, and (b3) an unsaturated compound having an oxetane skeleton as essential constituents A radiation-sensitive composition for forming a colored layer, comprising: A color comprising a colored layer formed through a step of irradiating a coating film of the radiation-sensitive composition for forming a colored layer with the radiation-sensitive composition for forming a colored layer according to claim 1. filter.   A color liquid crystal display device comprising the color filter according to claim 2.