JP4910792B2 - Radiation-sensitive composition for forming colored layer, color filter, and liquid crystal display device - Google Patents

Abstract

The invention supplies a radiation sensitive combination for forming the colouring layer of a colour filter. The radiation sensitive combination can restrain the pollution of the firing furnace and the photo mask caused by the sublimation of the radiation sensitive polymerization initiator, does not generate impurity in the liquid, with excellent developing performance and pattern shape. The radiation sensitive combination for forming the colouring layer contains (A) a colorant, (B) an alkali soluble resin, (C) a multifunctional monomer and (D) a radiation sensitive polymerization initiator taking the compound expressed by general formula (1) as component.

Description

  TECHNICAL FIELD The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display device, and more particularly useful for a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube device, and the like. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter having a colored layer formed from the radiation-sensitive composition, and a liquid crystal display device including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, the colored radiation-sensitive composition is applied onto a substrate or a substrate on which a light-shielding layer having a predetermined pattern has been previously formed, dried, and then applied. A formation method (see, for example, Patent Document 1 and Patent Document 2) is known in which a film is irradiated with radiation in a predetermined pattern shape (hereinafter referred to as “exposure”) and developed to obtain pixels of each color. Yes.
In recent years, the size of a mother glass substrate has been increased due to an increase in the area of a liquid crystal display panel and an improvement in productivity. However, with the increase in size of the substrate, the problem of contaminating the baking furnace and photomask due to the sublimation of the radiation-sensitive polymerization initiator component in the radiation-sensitive composition during the formation of the color filter has led to a reduction in production tact and production. Concerns have been raised because of the increased costs.

  Furthermore, the present applicant describes in Patent Document 3 as 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane-1 as a radiation-sensitive polymerization initiator of a radiation-sensitive composition. Radiation sensitive polymerization initiator components by using bromine substituted acetophenone compounds such as 1-one and 1- (3-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one It is disclosed that contamination of the baking furnace and exhaust duct due to sublimation of the filter, clogging of a filter provided in the development line when the developer is repeatedly used, and the like can be reduced.

JP-A-2-144502 JP-A-3-53201 JP 2001-235617 A

  However, in conventional radiation-sensitive compositions used for forming color filters, including those described in Patent Document 3, contamination of the firing furnace or photomask due to sublimation of the radiation-sensitive polymerization initiator component and foreign matter in liquid Development of a radiation-sensitive composition having both of these characteristics has been strongly desired.

  The problem of the present invention is that it can suppress contamination of the baking furnace, photomask, etc. due to sublimation of the radiation-sensitive polymerization initiator component, does not cause foreign matter in the liquid, and is excellent in developability, pattern shape, etc. It is providing the radiation sensitive composition used for formation of the colored layer of a color filter, a color filter provided with the colored layer formed from the said radiation sensitive composition, and a liquid crystal display panel provided with the said color filter.

The present invention, first,
Contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator having a compound represented by the following general formula (1) as essential components. A radiation-sensitive resin composition for forming a colored layer.

・・・・・・（１）

(1)

[In the formula (1), n is an integer of 2 to 12, and R ₁ is hydrogen, a hydroxyl group, or any group of structures represented by the following (I), (II), or (III): R ₂ in (III) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms). And may be substituted with at least one alkoxy group). ]

（Ｉ） （II） （III）

(I) (II) (III)

The present invention secondly,
A color filter comprising a colored layer formed from the radiation-sensitive composition for forming the colored layer.

Third, the present invention
A liquid crystal display panel including the color filter.

The radiation-sensitive resin composition for forming a colored layer of the present invention can suppress contamination of a baking furnace, a photomask, and the like due to sublimation of the radiation-sensitive polymerization initiator component, does not cause foreign matter in the liquid, and has a pixel pattern and It is possible to form a good pixel pattern and black matrix pattern without causing scum at the edge of the black matrix pattern and without undercut.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters and liquid crystal display panels including color filters for color liquid crystal display panels in the electronic industry. it can.

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

  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 Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Disperbyk (Bicchemy Japan Co., Ltd.), Sol Sparse (Seneca Co., Ltd.).
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.

-(B) Alkali-soluble resin-
As the alkali-soluble resin in the present invention, (A) acts as a binder for the colorant, and when producing a color filter, it is preferably used for the developer used in the development processing step, particularly preferably for the alkali developer. Although it will not specifically limit if it has solubility, The alkali-soluble resin which has a carboxyl group is preferable, and especially the ethylenically unsaturated monomer (henceforth "carboxyl group" which has one or more carboxyl groups). Containing unsaturated monomer ”) and other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as“ copolymerizable unsaturated monomer ”) (hereinafter referred to as“ carboxyl ”). Group-containing copolymer ").

As the carboxyl group-containing unsaturated monomer, for example,
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 carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are M-5300 and M-5400 (Toagosei Co., Ltd.), respectively. It is commercially available under the trade name of
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the copolymerizable unsaturated monomer 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-phenylmaleimide, N-cyclohexylmaleimide;

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 copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer in the present invention, (b1) (meth) acrylic acid is an essential component, and in some cases, succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meta). ) A carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group of acrylates, and (b2) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) Copolymerization with at least one copolymerizable unsaturated monomer selected from the group of acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Polymer (hereinafter referred to as “cal Cyclohexyl group-containing copolymer (B1) "hereinafter.) Are preferred.

As specific examples of the carboxyl group-containing copolymer (B1),
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / styrene / N-phenylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / styrene / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene / N-phenylmaleimide / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene / N-phenylmaleimide / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-phenylmaleimide / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-phenylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-cyclohexylmaleimide / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-cyclohexylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer and the like.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be reduced, whereas when it exceeds 50% by weight, the solubility in an alkali developer is low. When the development is performed with an alkaline developer, the colored layer tends to drop off from the substrate or the surface of the colored layer becomes rough.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000 to 300,000, preferably Is 5,000 to 100,000.
Further, 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 alkali-soluble resin in the present invention is usually from 3,000 to 60,000. , Preferably 5,000 to 25,000.
In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby pixels and black having sharp pattern edges can be obtained. A matrix can be formed, and residues, background stains, film residues, and the like are less likely to occur on the unexposed portion of the substrate and the light shielding layer during development.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1 to 5, and more preferably 1 to 4.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
The usage-amount of the alkali-soluble resin in this invention 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 amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. If the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, so that it may be difficult to achieve the target color density as a thin film.

-(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 (2)

Compound represented by the following formula (3)

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

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 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 the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin, and N- (meth). In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, examples of 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 contains the compound represented by the general formula (1) (hereinafter referred to as “compound 1”) as an essential component, and the (C) polyfunctional monomer and optionally the case by exposure. It has the effect | action which produces the active species which can start superposition | polymerization of the monofunctional monomer used.

In the formula (1), n is an integer of 2 to 12, and R ₁ is a hydrogen atom, a hydroxyl group, or any group having the structure represented by the above (I), (II), or (III). R ₂ in (III) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms). And may be substituted with at least one alkoxy group).
Here, examples of the alkyl group having 1 to 12 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms of R ₂ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Examples thereof include an n-dodecyl group, a cyclopentyl group, and a cyclohexyl group.

  Moreover, as a C1-C6 alkyl group substituted by a phenyl group, a C1-C6 alkoxy group, as a C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, As an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and an alkoxy group having 1 to 6 carbon atoms, for example, Examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a t-butoxy group.

Specific examples of preferred compound (1) in the present invention include
2-methyl-1- [4- (ethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-propylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (i-propylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (i-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (t-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-pentylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-hexylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-heptylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-octylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-dodecylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-hydroxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-hydroxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (5-hydroxyheptylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (5-hydroxyhexylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-methacryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-acryloyloxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-methacryloyloxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-acryloyloxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-methacryloyloxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acetylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acetylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-propionylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-butyrylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-valerylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-hexanoylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-benzoylethylthio) phenyl] -2-morpholinopropan-1-one,
And 2-methyl-1- [4- (4-acetylbutylthio) phenyl] -2-morpholinopropan-1-one.

Of these compounds (1), in particular, 2-methyl-1- [4- (ethylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (n-propylthio) phenyl] 2-morpholinopropan-1-one, 2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (2-hydroxyethyl) Thio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (3-hydroxybutylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4 -(2-acryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (2-methacryloyloxyethylthio) phenyl] -2-morpho Nopuropan-1-one, 2-methyl-1- [4- (4-acetyl-butyl) phenyl] -2-morpholino-1-one are preferred.
In this invention, a compound (1) can be used individually or in mixture of 2 or more types.

In the present invention, other radiation-sensitive polymerization initiators (hereinafter referred to as “other polymerization initiators”) may be used in combination with the polymerization initiator (1).
Other polymerization initiators include, for example, biimidazole compounds, acetophenone compounds, benzophenone compounds, benzoins having at least one main skeleton represented by the following formula (4), formula (5) or formula (6) Compound, α-diketone compound, polynuclear quinone compound, xanthone compound, phosphine compound, triazine compound, carbazole compound, etc., among which biimidazole compound, acetophenone compound and the like are preferable. .

As a specific example of the biimidazole compound,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-
1,2'-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

Of these biimidazole compounds, 2,2′-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole and 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole are preferred, especially 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole is preferred.
The biimidazole compounds can be used alone or in admixture of two or more.

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

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

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

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

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples include ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable. In addition, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone can act as radiation-sensitive polymerization initiators alone even when no biimidazole compound is present. It is.

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

Specific examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane. -1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (methylthio) phenyl] -2-methyl-2-morpholinopropane- 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1 -(2-Bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1- (4-morph Linophenyl) -2- (2-bromobenzyl) -2-dimethylaminobutan-1-one, 1- (4-morpholinophenyl) -2- (4-bromobenzyl) -2-dimethylaminobutan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.
Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1- (4-morpholinophenyl) -2-benzyl-2-dimethyl Aminobutan-1-one, 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1- (4-morpholinophenyl) -2- (4- Bromobenzyl) -2-dimethylaminobutan-1-one and the like are preferable.
In the present invention, also when an acetophenone-based compound is used in combination as another polymerization initiator, one or more hydrogen donors can be added.

Specific examples of the benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl-2-benzoyl benzoate.
Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate, and the like.
Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Specific examples of the xanthone compound include xanthone, thioxanthone, and 2-chlorothioxanthone.
Specific examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (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- Kishisuchiriru) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

Compound represented by the following formula (7)

Compound represented by the following formula (8)

And triazine compounds having a halomethyl group.

Moreover, as a specific example of the said carbazole type compound, for example, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9. H. -Carbazol-3-yl] ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl ] -9. H. -Carbazol-3-yl]-, 1- (O-ostyloxime) and the like.
Among these carbazole compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] ethane-1-one oxime-O-acetate, ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl ] -9. H. -Carbazol-3-yl]-, 1- (O-octyloxime) is preferred.

  These other polymerization initiators can be used alone or in admixture of two or more. The use ratio of the other polymerization initiator is usually 80% by weight or less, more preferably 70% by weight or less based on the total of the polymerization initiator (1) and the other polymerization initiator. In this case, when the proportion of other polymerization initiator used exceeds 95% by weight, the intended effect of the present invention may be impaired.

The amount of the polymerization initiator used in the present invention is usually 0.01 to 200 parts by weight, preferably 1 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. ˜120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the amount of the polymerization initiator used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds 200 parts by weight, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking / sensitizer can be used in combination with the radiation-sensitive polymerization initiator, if necessary.

-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, which has an action of improving the solubility characteristics of the radiation-sensitive composition for forming a colored layer in an alkaline developer and further suppressing the remaining of undissolved material after development. And compounds (excluding the hydrogen donor).

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 phenyl group-containing carboxylic acids include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

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

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.
Examples of phenyl group-containing amines include:
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, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of a colored layer to fall.

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-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

-Solvent-
The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and optionally contains the additive component, but usually contains a solvent as a liquid composition. Prepared.
The solvent may be appropriately selected and used as long as each component constituting the radiation-sensitive composition is dispersed or dissolved and does not react with these components and has appropriate volatility. it can.

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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.

  The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the 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 has a colored layer formed from the radiation-sensitive composition for forming a colored layer of the present invention.
The method for forming the color filter of the present invention will be described below.
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.
The black matrix can be formed in the same manner as in the pixel formation using the radiation-sensitive composition for forming a colored layer of the present invention.

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.

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

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
<(B) Production of alkali-soluble resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 15 parts by weight of styrene. , 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 25 parts by weight of N-phenylmaleimide and 2.5 parts by weight of chain transfer agent α-methylstyrene dimer were substituted with nitrogen, and then gently stirred. The temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour, whereby (B) alkali A solution of a soluble resin (solid content concentration = 33.0%) was obtained.
This (B) alkali-soluble resin had Mw = 17,000 and Mn = 8,000. This (B) alkali-soluble resin is referred to as “resin (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 15 parts by weight of styrene. Part, 10 parts by weight of benzyl methacrylate, 20 parts by weight of n-butyl methacrylate, 25 parts by weight of N-phenylmaleimide, 15 parts by weight of hydroxyethyl melacrylate and 5 parts by weight of chain transfer agent α-methylstyrene dimer were substituted 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 polymerization for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour, whereby (B) alkali A soluble resin solution (solid content concentration = 32.9%) was obtained.
This (B) alkali-soluble resin was Mw = 11,000 and Mn = 6,700. This (B) alkali-soluble resin is referred to as “resin (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 15 parts by weight of styrene. Parts, benzyl methacrylate 30 parts by weight, glycerol monomethacrylate 10 parts by weight, N-phenylmaleimide 30 parts by weight and chain transfer agent α-methylstyrene dimer 2.5 parts by weight, and after nitrogen substitution, gently stirring, The temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour, whereby (B) alkali A solution of a soluble resin (solid content concentration = 33.2%) was obtained.
This (B) alkali-soluble resin had Mw = 15,000 and Mn = 7,000. This (B) alkali-soluble resin is referred to as “resin (B-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 30 parts by weight of acenaphthylene. , 35 parts by weight of benzyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate and 5 parts by weight of chain transfer agent α-methylstyrene dimer were substituted with nitrogen, and then gently stirred. Then, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour, whereby (B) alkali A solution of a soluble resin (solid content concentration = 31.0%) was obtained.
This (B) alkali-soluble resin had Mw = 10,000 and Mn = 6,000. This (B) alkali-soluble resin is referred to as “resin (B-4)”.

Example 1
(A) 85 parts by weight of a 80/20 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Red 177 as a colorant, (B) 70 parts by weight of a resin (B-1) as an alkali-soluble resin, and (C) many 80 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, and (D) 2-methyl-1- [4- (hydroxyethylthio) phenyl] -2-morpholinopropane-1- as a radiation-sensitive polymerization initiator 50 parts by weight of ON and 1,000 parts by weight of a 70/30 (weight ratio) mixture of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate as a solvent were mixed to give a liquid composition ( R1) was prepared.

<Formation of colored layer>
The liquid composition (R1) was applied to a soda glass substrate with a SiO2 film formed on the surface to prevent elution of sodium ions using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 2 minutes. A film having a thickness of 1.7 μm was formed.
Next, after cooling the substrate to room temperature, ultraviolet rays containing 365 nm, 405 nm, and 436 nm were applied to the coating film through a photomask (slit width of 30 microns) using a high-pressure mercury lamp at 5,000 J / m ^2. The exposure amount was as follows. Thereafter, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a pixel array composed of red stripe pixels on the substrate.

Evaluation of developability The pixel array was observed with an optical microscope. As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. The remaining film ratio of the pixel array was as good as 80%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Evaluation of sublimation The liquid composition (R1) was applied on a substrate and then dried to form a coating film having a thickness of 1.7 μm. Thereafter, for this coating film, n-octane (specific gravity = 0.701, injection amount = 0.02 μL) was used as the standard substance, the purge condition was 100 ° C./10 minutes, and the headspace sampler was JHS-100A (product Name, manufactured by Nihon Analytical Industrial Co., Ltd.) and headspace gas chromatography using a JEOL JMS-AX505W type mass spectrometer (trade name, manufactured by Nihon Analytical Industrial Co., Ltd.) as a gas chromatography / mass spectrometer. / Mass spectrometry was performed, (D) the peak area A derived from the radiation-sensitive polymerization initiator component was determined, and the volatilization amount in terms of n-octane was calculated according to the following formula. The volatilization amount was 0 μg. . <Calculation formula for volatilization by n-octane conversion>
Volatilization amount (μg)
= A × (amount of n-octane) (μg) / (peak area of n-octane)

Evaluation of foreign matter in liquid After storing the liquid composition (R1) at 5 ° C. for 7 days, the presence or absence of a recrystallized product of (D) radiation-sensitive polymerization initiator component was visually observed. Further, when the temperature of the liquid composition (R1) after storage is raised from 5 ° C. to 23 ° C., a solid having a size of 0.5 μm or more remaining without being redissolved in 1 ml of the liquid composition (R1). When the number of objects (foreign matter in liquid) was measured using a light scattering type in-liquid particle detector (trade name KS-28B, manufactured by Rion Co., Ltd.), no solid matter was observed.

Example 2
(D) The same as Example 1 except that 50 parts by weight of 2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one was used as the radiation-sensitive polymerization initiator. Thus, a liquid composition (R2) of a radiation sensitive composition was prepared.
Next, a pixel array composed of red stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. Further, the remaining film ratio of the pixel array was as good as 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid.

Comparative Example 1
Except for using 50 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals) as a radiation-sensitive polymerization initiator. In the same manner as in Example 1, a liquid composition (r1) of a radiation sensitive composition was prepared.
Next, a pixel array composed of red stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (r1) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, the residual film ratio of the pixel array was 79%, and the cross section of the pixel pattern was observed with a scanning electron microscope (SEM). Although no liquid foreign matter was observed, scum or chipping was observed at the edge of the pixel pattern, and the volatilization amount of the coating film was 1.0 μg.

Example 3
(A) 95 parts by weight of a 60/40 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as a colorant, (B) 70 parts by weight of a resin (B-2) as an alkali-soluble resin, and (C) many 80 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, and (D) 2-methyl-1- [4- (hydroxyethylthio) phenyl] -2-morpholinopropane-1- as a radiation-sensitive polymerization initiator 50 parts by weight of ON, 1 part by weight of malonic acid as an additive, and 900 parts by weight of a 50/50 (weight ratio) mixture of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate as a solvent were mixed to produce a radiation sensitive composition. A liquid composition (G1) was prepared.
Next, a pixel array composed of green stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (G1) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. The remaining film ratio of the pixel array was as good as 80%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid.

Comparative Example 2
Radiation sensitivity was obtained in the same manner as in Example 3, except that 50 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one was used as the radiation sensitive polymerization initiator. A liquid composition (g1) of the composition was prepared.
Next, a pixel array composed of green stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (g1) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, the residual film ratio of the pixel array was 79%, and the cross section of the pixel pattern was observed with a scanning electron microscope (SEM). Although no liquid foreign matter was observed, scum or chipping was observed at the edge of the pixel pattern, and the volatilization amount of the coating film was 1.0 μg.

Example 4
(A) 70 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, (B) 60 parts by weight of a resin (B-3) as an alkali-soluble resin, (C ) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-methyl-1- [4- (hydroxyethylthio) phenyl] -2-morpholinopropane- as a radiation sensitive polymerization initiator 50 parts by weight of 1-one, 5 parts by weight of a nonionic surfactant A-60 (trade name, manufactured by Kao Corporation) as an additive, and 60 of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate as a solvent A liquid composition (B1) of a radiation sensitive composition was prepared by mixing 900 parts by weight of a / 40 (weight ratio) mixture.
Next, a pixel array composed of blue stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (B1) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. Further, the remaining film ratio of the pixel array was as good as 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid.

Example 5
(D) 15 parts by weight of 2-methyl-1- [4- (hydroxyethylthio) phenyl] -2-morpholinopropan-1-one as a radiation-sensitive polymerization initiator, 2,2′-bis (2-chlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole 6 parts by weight, 4,4'-bis (diethylamino) benzophenone 9 parts by weight as an amine hydrogen donor, mercaptan hydrogen donation Example 3 except that 3 parts by weight of 2-mercaptobenzothiazole and 15 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one were used as the body. Thus, a liquid composition (B2) of a radiation sensitive composition was prepared.
Next, a pixel array composed of blue stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (B2) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. Further, the remaining film ratio of the pixel array was as good as 90%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid.

Comparative Example 3
Radiation sensitivity was obtained in the same manner as in Example 3, except that 50 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one was used as the radiation sensitive polymerization initiator. A liquid composition (b1) of the composition was prepared.
Next, a pixel array composed of blue stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (b1) was used instead of the liquid composition (R1). went.
As a result, no development residue is observed on the unexposed substrate, no scum or chipping is observed at the edge of the pixel pattern, the residual film ratio of the pixel array is 84%, and the volatilization amount of the coating film is 0 μg. Although no foreign matter was observed in the liquid, the undercut was observed when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM).

Example 6
(A) Carbon black (manufactured by Mikuni Dye Co., Ltd.) 250 parts by weight as a colorant, (B) 75 parts by weight of resin (B-4) as an alkali-soluble resin, and (C) dipentaerythritol as a polyfunctional monomer 75 parts by weight of hexaacrylate, (D) 50 parts by weight of 2-methyl-1- [4- (hydroxyethylthio) phenyl] -2-morpholinopropan-1-one as a radiation-sensitive polymerization initiator, and propylene as a solvent A liquid composition (BK1) of a radiation sensitive composition was prepared by mixing 1,000 parts by weight of a 50/50 (weight ratio) mixture of glycol monomethyl ether acetate and cyclohexanone.
Next, a pixel array composed of black stripe pixels was formed on the substrate in the same manner as in Example 1 except that the liquid composition (BK1) was used instead of the liquid composition (R1). went.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. The remaining film ratio of the pixel array was as good as 80%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid. Moreover, the adhesion of the pixel to the substrate was also excellent.

Comparative Example 4
As a radiation-sensitive polymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 30 parts by weight, 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5'-tetraphenyl-1,2'-biimidazole, 12 parts by weight of 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor, and 2-mercapto as a mercaptan hydrogen donor A liquid composition (bk1) of a radiation sensitive composition was prepared in the same manner as in Example 7 except that 6 parts by weight of benzothiazole was used.
Next, except that the liquid composition (bk1) was used instead of the liquid composition (BK1), a pixel array composed of black stripe pixels was formed on the substrate in the same manner as in Example 1, and the evaluation was performed. went.
As a result, no development residue was observed on the unexposed portion of the substrate, the residual film ratio of the pixel array was 83%, and the volatilization amount of the coating film was 0 μg. Chipping was observed, and the cross section of the pixel pattern was observed with a scanning electron microscope (SEM). As a result, undercuts were observed and five foreign matters were observed in the liquid.

Example 7
The liquid composition of the radiation-sensitive composition was the same as in Example 1 except that 1,500 parts by weight of a 70/30 (weight ratio) mixture of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate was used as the solvent. Composition (R2) was prepared.
Next, a red stripe was formed on the substrate in the same manner as in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1), and a slit die coater was used instead of the spin coater. A pixel array composed of pixel-like pixels was formed and evaluated.
As a result, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed at the edge of the pixel pattern. Further, the remaining film ratio of the pixel array was as good as 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed. Moreover, the volatilization amount of the coating film was 0 μg, and no foreign matter was observed in the liquid.

Claims (5)

Contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator having a compound represented by the following formula (1) as essential components. A radiation-sensitive composition for forming a colored layer.

[In Formula (1), n is an integer of 2 to 12, and R ₁ is any _one of a hydrogen atom, a hydroxyl group, or a structure represented by the following (I), (II), or (III): R ₂ in (III) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, 6 may be substituted with at least one alkoxy group). ]

  A color filter having a colored layer formed from the radiation-sensitive composition for forming a colored layer according to claim 1.   A liquid crystal display device comprising the color filter according to claim 2. Forming a coating film of the radiation-sensitive composition for forming a colored layer according to claim 1, exposing the coating film through a photomask, developing with an alkaline developer, and then post-baking A feature pixel forming method. A color filter is formed from a radiation-sensitive composition for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator. In this case, (D) a radiation-sensitive polymerization initiator containing a compound represented by the following formula (1) as an essential component is used as a radiation-sensitive polymerization initiator. A method for preventing contamination of a baking furnace or a photomask and generation of foreign matter in liquid due to sublimation of a radiation-sensitive polymerization initiator component when forming a filter.

[In Formula (1), n is an integer of 2-12, R ₁ Represents a hydrogen atom, a hydroxyl group, or any group having the structure represented by the following (I), (II), or (III), and R in (III) ₂ Is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (however, at least one of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms) May be substituted). ]