TWI459133B - Radiation sensitive composition for formation of colouring layer, color filter and color liquid crystal display element - Google Patents

Description

Radiation-sensitive composition for coloring layer formation, color filter, and color liquid crystal display element

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a liquid crystal display element, and more particularly to a color filter used in a transmissive or reflective type color liquid crystal display device, a color image tube element, or the like. A color filter for forming a coloring layer suitable for use in a sheet, a color filter having a coloring layer formed using the radiation-sensitive composition, and a color liquid crystal display element having the color filter.

As a method of forming a color filter using a coloring sensitizing radiation composition, it is known that a color-sensitive radiation composition coating film is formed on a substrate or a substrate on which a desired pattern-like light-shielding layer is formed in advance, by having a desired The mask of the pattern is irradiated with radiation (hereinafter referred to as "exposure"), and developed to dissolve and remove the unexposed portion, and then post-baking to obtain each color pixel (refer to, for example, Patent Document 1 and Patent Document 2). Further, a method of forming a black matrix using a photopolymerizable composition containing a black material is also known (refer to, for example, Patent Document 3).

Further, in recent years, in the field of color filter technology, it has become a mainstream to reduce the amount of exposure to shorten the tact time. Therefore, it is required to have sufficient development resistance, solvent resistance, and the like even at a low exposure amount, that is, a feeling of forming a colored layer. High sensitivity to radioactive compositions. In particular, with respect to solvent resistance, since cracks or chips in the pixel pattern and the elution of the coloring component in the pixel pattern are increasingly prominent, it is necessary to solve the problem. The background of such a problem is considered to be in response to recent demands for high contrast, high brightness, and high color purification of color liquid crystal display elements, and most of the pigments used in the radiation sensitive composition for forming a colored layer are used. Various kinds of refining treatments or surface treatments, and the content ratio of the pigment in the radiation-sensitive composition for coloring layer formation tend to be higher and higher.

Further, for example, in Patent Documents 4 to 6, in order to improve the solvent resistance of the pixel pattern formed using the radiation sensitive composition, a binder polymer having an oxetane skeleton is proposed. However, in such a radiation-sensitive composition, if the exposure amount is lowered or a specific pigment is used, sufficient development resistance and solvent resistance cannot be obtained.

(Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 2-144502

Patent Document 2: Japanese Patent Laid-Open No. 3-53201

Patent Document 3: Japanese Patent Laid-Open No. Hei 6-35188

Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-296778

Patent Document 5: Japanese Patent Laid-Open Publication No. 2007-316485

Patent Document 6: Japanese Laid-Open Patent Publication No. 2007-316506

An object of the present invention is to provide a radiation-sensitive composition for forming a coloring layer capable of forming a pixel and a black matrix which have sufficient development resistance and low solvent resistance even at a low exposure amount.

Another object of the present invention is to provide a color filter having a pixel formed of the radiation sensitive composition for a color filter, and a color liquid crystal display element having the color filter.

As a result of intensive studies, the present inventors have found that the above problems can be solved by including a polymer having an oxetane group and a polymerizable unsaturated bond, and completed the present invention.

That is, the first aspect of the present invention provides a radiation sensitive composition for forming a coloring layer, characterized by comprising (A) a coloring agent, (B) a polymer having an oxetane group and a polymerizable unsaturated bond, and (C) Photopolymerization initiator.

The term "radiation" as used in the present invention means a radiation containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

The second aspect of the present invention provides a color filter having a coloring layer formed using the photosensitive layer-forming radiation sensitive composition, and a color liquid crystal display element having the color filter.

The radiation sensitive composition of the present invention can form a pixel and a black matrix which have sufficient development resistance even in a low exposure amount and are excellent in solvent resistance. The development resistance and solvent resistance are the same as those of the composition containing the copolymer having only the oxetane group described in Patent Documents 4 to 6 or the copolymer having no oxetane group. The situation of the object is significantly superior.

Best form for implementing the invention

Hereinafter, the present invention will be described in detail.

Sensitive radioactive composition for coloring layer formation

The "colored layer" in the radiation-sensitive composition for coloring layer formation (hereinafter also simply referred to as "radiation-sensitive linear composition") of the present invention means that the pixel and/or black matrix used in the color filter is composed of a color filter. Layer.

Hereinafter, the constituent components of the radiation sensitive composition for forming a colored layer of the present invention will be described.

- (A) colorant -

The coloring agent (A) in the present invention is not particularly limited in color tone, and may be appropriately selected depending on the use of the obtained color filter, and a pigment, a dye or a natural pigment may be used. Since the color filter is required to have heat resistance, the coloring agent in the present invention is preferably an organic pigment or an inorganic pigment.

As the above-mentioned organic pigment, for example, a pigment index (CI; published by The Society of Dyers and Colourists) can be cited as a pigment (Pigment), and specifically, a pigment index (CI) number with the following pigments can be cited. Compound.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI. Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123 , CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI pigment purple 38; CI pigment blue 15, CI pigment blue 15:3, CI pigment blue 15:4, CI pigment blue 15:6, CI pigment blue 60, CI pigment blue 80; CI pigment green 7, CI pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.

In the present invention, the organic pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Further, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, and iron blue. Chromium oxide green, cobalt green, alumina, titanium black, synthetic iron black, carbon black, and the like.

These colorants can also be modified with a polymer as needed on the surface of the particles. Examples of the polymer of the surface of the modified pigment particle include a polymer described in JP-A-H08-259876, or a commercially available polymer or oligomer for pigment dispersion. A method of coating the surface of the carbon black is disclosed in, for example, JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like.

The above colorants may be used singly or in combination of two or more.

When the radiation sensitive composition of the present invention is used for forming a pixel, since the pixel requires high-definition color development, the coloring agent (A) is preferably a coloring agent having a high color developability, specifically, It is preferred to use an organic pigment.

Further, when the radiation sensitive composition of the present invention is used to form a black matrix, since the black matrix is required to have light blocking properties, it is preferred to use an organic pigment or carbon black as the (A) coloring agent.

Further, the radiation sensitive composition of the present invention is particularly useful for improving the solvent resistance of a coloring layer formed using a radiation sensitive composition containing a color selected from CI Pigment Red 254 and CI Pigment Green 58. At least one of the group consisting of carbon black is used as the (A) colorant.

The radiation sensitive composition of the present invention has excellent solvent resistance even when the content of the colorant reaches 30% by weight or more of the total solid content of the radiation sensitive composition. In the present invention, the upper limit of the content of the colorant is preferably 70% by weight or less, and particularly preferably 60% by weight or less, based on the total solid content of the radiation sensitive composition from the viewpoint of ensuring developability. Here, the solid component means a component other than the following solvent.

The coloring agent in the present invention may be used together with a dispersing agent or a dispersing aid as needed.

As the dispersing agent, for example, a suitable dispersing agent such as a cationic substance, an anionic type, a nonionic type or an amphoteric type can be used, and a polymer dispersing agent is preferable. Specific examples thereof include an alkyl amide salt or a phosphate salt of a modified acrylic copolymer, an acrylic copolymer, a polyurethane, a polyester, a polymer copolymer, a cationic comb-type graft polymer, and the like. . Here, the term "cationic comb-type graft polymer" refers to a structure having a branched polymer having two or more molecules on a main chain polymer having a plurality of basic groups (cationic functional groups) in one molecule. The polymer may, for example, be a polymer composed of a polyethyleneimine having a main chain polymer portion and a ring-opening polymer having a branched polymer portion of ε-caprolactone. Among these dispersants, preferred are modified acrylic copolymers, polyurethanes, and cationic comb-type graft polymers.

Such a dispersing agent is commercially available. For example, as a modified acrylic polymer, Disperbyk-2000, Disperbyk-2001 (above, BYK-Chemie (BYK)) can be cited as a polyurethane, and List Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK-Chemie (BYK)), SOLSPERSE 76500 (manufactured by LUBRIZOL Co., Ltd.) Examples of the cationic comb-type graft polymer include SOLSPERSE 24000 (manufactured by LUBRIZOL Co., Ltd.), AJISPER PB 821, AJISPER PB 822, AJISPER PB 880 (manufactured by Ajinomoto FineTechno Co., Ltd.), and the like.

These dispersing agents may be used alone or in combination of two or more. The content of the dispersant 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 preferably 10 to 50 parts by weight, per 100 parts by weight of the (A) coloring agent. If the content of the dispersant is too large, there is a risk of impairing developability and the like.

The dispersing aid may, for example, be a blue pigment derivative or a yellow pigment derivative, and specific examples thereof include a copper phthalocyanine derivative.

- (B) a polymer having an oxetane group and a polymerizable unsaturated bond -

(B) a polymer having an oxetane group and a polymerizable unsaturated bond (hereinafter also referred to as "polymer (B)") in the present invention is a crosslinking reaction occurring in the exposure and post-baking steps A component that hardens the coating film. When the radiation-sensitive composition of the present invention contains the polymer (B), it is possible to form a coloring layer which is excellent in development resistance and solvent resistance even in the case of a low exposure amount.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B) is preferably 3,000 to 50,000, more preferably 5,000. 30000.

In addition, the ratio (Mw/Mn) of the Mw of the polymer (B) to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), It is preferably 1 to 5, more preferably 1 to 4. If the Mw is too small, there is a risk that the desired effect cannot be obtained. On the other hand, if it is too large, there is a risk that scallops, residual film, and the like may be generated on the unexposed portion of the substrate or on the light shielding layer.

The oxetane group in the polymer (B) may further have a substituent. Examples of the substituent include fluorine, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a perfluoroalkyl group having 1 to 4 carbon atoms. The polymer (B) is preferably a repeating unit represented by the following formula (1).

(wherein Z represents -O-, -CO-, -C(=O)O-(*), -CONH-(*) (where "*" is a linkage to A) or phenyl , A represents a group having an oxetane group, and R ⁷ represents a hydrogen atom or a methyl group).

Further, examples of the polymerizable unsaturated bond in the polymer (B) include a vinyl group, a (meth)acryl fluorenyl group, an allyl group, and the like, and a (meth) acrylonitrile group is preferable. Further, the polymer (B) preferably has a polymerizable unsaturated bond in its side chain.

The polymer (B) preferably has 0.1 to 5.0 mmol/g oxetanyl group and 0.1 to 5.0 mmol/g (meth) propylene oxime from the viewpoint of development resistance and solvent resistance. The polymer of the base is more preferably a polymer having 0.3 to 4.0 mmol/g oxetanyl group and 0.3 to 4.0 mmol/g (meth) acryl fluorenyl group, and the particularly preferred system has 0.3 to 2.5. A millimol/g oxetane group and a polymer of 0.5 to 4.0 millimoles per gram of (meth)acrylonitrile.

The polymer (B) is not particularly limited as long as it satisfies the above conditions, and for example, it may be selected from

(B-1) a copolymer comprising a monomer comprising (b1) a polymerizable unsaturated compound having an oxetanyl group and (b2) a polymerizable unsaturated compound having a hydroxyl group (hereinafter also referred to as "first" a polymer obtained by reacting a copolymer (1)") with (b3) an unsaturated isocyanate compound (hereinafter also referred to as "polymer (B-1)"),

(B-2) a copolymer containing a monomer composed of (b1) a polymerizable unsaturated compound having an oxetanyl group and (b4) an unsaturated carboxylic acid (hereinafter also referred to as "proline copolymer ( 2)") a polymer obtained by reacting (b5) a polymerizable unsaturated compound having an oxirane group (hereinafter also referred to as "polymer (B-2)"), and

(B-3) a copolymer of a monomer comprising (b1) a polymerizable unsaturated compound having an oxetanyl group and (b5) a polymerizable unsaturated compound having an oxirane group (hereinafter also At least one of the group consisting of a polymer obtained by reacting a "precursor copolymer (3)") with (b4) an unsaturated carboxylic acid (hereinafter also referred to as "polymer (B-3)").

Hereinafter, (b1) a polymerizable unsaturated compound having an oxetanyl group, (b2) a polymerizable unsaturated compound having a hydroxyl group, (b3) an unsaturated isocyanate compound, (b4) an unsaturated carboxylic acid, and (b5) Polymerizable unsaturated compounds having an oxiranyl group, also referred to as "compound (b1)", "compound (b2)", "compound (b3)", "compound (b4)", and "compound (b5), respectively) ". Further, the polymerizable unsaturated compound other than the above compounds (b1) to (b5) is hereinafter also referred to as "compound (b6)".

The compound (b1) may, for example, be 3-(vinyloxymethyl)-2-methyloxetane or 3-(vinyloxymethyl)-3-methyloxetane. Alkanes, 3-(vinyloxymethyl)-2-ethyloxetane, 3-(vinyloxymethyl)-3-ethyloxetane, 3-(vinyloxy Benzyl)-2-methyloxetane, 3-(vinyloxyethyl)-3-methyloxetane, 3-(vinyloxyethyl)-2-ethyl Oxycyclobutane, 3-(vinyloxyethyl)-3-ethyloxetane, 2-(vinyloxymethyl)-2-methyloxetane, 2 -(vinyloxymethyl)-3-methyloxetane, 2-(vinyloxymethyl)-2-ethyloxetane, 2-(vinyloxymethyl -3-ethyloxetane, 2-(vinyloxyethyl)-2-methyloxetane, 2-(vinyloxyethyl)-3-methyloxa Cyclobutane, 2-(vinyloxyethyl)-2-ethyloxetane, 2-(vinyloxyethyl)-3-ethyloxetane, etc. (vinyl oxygen Alkyl)alkyloxetane; 3-[(meth)acryloxymethyl]oxetane, 3-[2-(methyl)propene oxime Ethylethyl]oxetane, 2-[(meth)acryloxymethyl]oxetane, 2-[2-(methyl)propenyloxyethyl]oxetane (meth) propylene oxiranyl oxetane, 3-[(methyl) propylene methoxymethyl]-2-methyl oxetane, 3-[(methyl) Propylene methoxymethyl]-3-methyloxetane, 3-[(meth)acryloxymethyl]-2-ethyloxetane, 3-[(methyl) Propylene methoxymethyl]-3-ethyloxetane, 3-[2-(methyl)propenyloxyethyl]-2-methyloxetane, 3-[2- (Meth) propylene methoxyethyl]-3-methyl oxetane, 3-[2-(methyl) propylene methoxyethyl]-2-ethyl oxetane, 3 -[2-(Methyl)acryloxyethyl]-3-ethyloxetane, 2-[(meth)acryloxymethyl]-2-methyloxetane 2-[(Meth)acryloxymethyl]-3-methyloxetane, 2-[(methyl)acryloxymethyl]-4-methyloxetane , 2-[(Meth)acryloxymethyl]-2-ethyloxetane, 2-[(meth)acryloxymethyl]-3-ethyloxetane 2-[(Meth) propylene methoxymethyl ]-4-Ethyloxetane, 2-[2-(methyl)propenyloxyethyl]-2-methyloxetane, 2-[2-(methyl)propene oxime Oxyethyl]-3-methyloxetane, 2-[2-(methyl)propenyloxyethyl]-4-methyloxetane, 2-[2-(A Acetyloxyethyl]-2-ethyloxetane, 2-[2-(methyl)propenyloxyethyl]-3-ethyloxetane, 2-[ 2-(methyl)acryloxyethyl]-4-ethyloxetane and the like [(meth)acryloxyalkyl]alkyloxetane; 3-[(methyl ) propylene methoxymethyl]-2-trifluoromethyl oxetane, 3-[(methyl) propylene methoxymethyl]-2-pentafluoroethyl oxetane, 3- [(Meth)acryloxymethyl]-2-fluorooxetane, 3-[(meth)acryloxymethyl]-2,2-difluorooxetane, 3 -[(Meth)acryloxymethyl]-2,2,4-trifluorooxetane, 3-[(meth)acryloxymethyl]-2,2,4,4 -tetrafluorooxetane, 3-[2-(methyl)acryloxyethyl]-2-trifluoromethyloxetane, 3-[2-(methyl)propene oxime 5-ethyl 5-pentafluoroethyl oxetane, 3-[2-(methyl) propylene oxime Ethyl]-2-fluorooxetane, 3-[2-(methyl)propenyloxyethyl]-2,2-difluorooxetane, 3-[2-(methyl ) propylene methoxyethyl]-2,2,4-trifluorooxetane, 3-[2-(methyl) propylene methoxyethyl]-2,2,4,4-tetrafluoro Oxetane, 2-[(meth)acryloxymethyl]-2-trifluoromethyloxetane, 2-[(meth)acryloxymethyl]-3- Trifluoromethyloxetane, 2-[(meth)acryloxymethyl]-4-trifluoromethyloxetane, 2-[(meth)propenyloxymethyl ]-2-pentafluoroethyl oxetane, 2-[(meth) propylene methoxymethyl]-3-pentafluoroethyl oxetane, 2-[(meth) propylene oxime Oxymethyl]-4-pentafluoroethyloxetane, 2-[(meth)acryloxymethyl]-2,3-difluorooxetane, 2-[(A Base) propylene methoxymethyl]-2,4-difluorooxetane, 2-[(meth)acryloxymethyl]-3,3-difluorooxetane, 2 -[(Meth)acryloxymethyl]-3,4-difluorooxetane, 2-[(meth)acryloxymethyl]-4,4-difluorooxocycle Butane, 2-[(meth)acryloxymethyl]-3,3,4-trifluorooxetane, 2 -[(Meth)acryloxymethyl]-3,4,4-trifluorooxetane, 2-[(meth)acryloxymethyl]-3,3,4,4 -tetrafluorooxetane, 2-[2-(methyl)acryloxyethyl]-2-trifluoromethyloxetane, 2-[2-(methyl)propene oxime Ethylethyl]-3-trifluoromethyloxetane, 2-[2-(methyl)propenyloxyethyl]-4-trifluoromethyloxetane, 2-[2 -(Methyl)acryloxyethyl)-2-pentafluoroethyloxetane, 2-[2-(methyl)propenyloxyethyl]-3-pentafluoroethyloxy Cyclobutane, 2-[2-(methyl)propenyloxyethyl]-4-pentafluoroethyloxetane, 2-[2-(methyl)propenyloxyethyl]- 2,3-Difluorooxetane, 2-[2-(methyl)propenyloxyethyl]-2,4-difluorooxetane, 2-[2-(methyl) Propylene methoxyethyl]-3,3-difluorooxetane, 2-[2-(methyl)propenyloxyethyl]-3,4-difluorooxetane, 2 -[2-(Methyl)acryloxyethyl)-4,4-difluorooxetane, 2-[2-(methyl)propenyloxyethyl]-3,3,4 -trifluorooxetane, 2-[2-(methyl)propenyloxyethyl]-3,4,4-trifluorooxetane, 2-[2-(A [(Meth) propylene methoxyalkyl] fluorooxetane or [(meth) propylene] propylene methoxyethyl]-3,3,4,4-tetrafluoro oxetane醯 oxyalkyl] fluoroalkyl oxetane; 2-[(meth) propylene methoxymethyl]-2-phenyl oxetane, 2-[(meth) propylene oxime Oxymethyl]-3-phenyloxetane, 2-[(meth)acryloxymethyl]-4-phenyloxetane, 2-[2-(methyl) Propylene methoxyethyl]-2-phenyl oxetane, 2-[2-(methyl) propylene methoxyethyl]-3-phenyl oxetane, 2-[2- [(meth)acryloxyethyl]-4-phenyloxetane and the like [(meth)acryloxyalkyl]phenyloxetane; 4-[3-(3- Ethyloxetane-3-ylmethoxy)propoxy]styrene, 4-[4-(3-ethyloxetan-3-ylmethoxy)butoxy]benzene Ethylene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, 4-[6-(3-ethyloxetane-3- An oxetanyl group such as methoxy)hexyloxy]styrene or 4-[7-(3-ethyloxetan-3-ylmethoxy)heptyloxy]styrene An aromatic vinyl compound or the like.

Among these compounds (b1), 3-(vinyloxymethyl)-3-ethyloxetane and 3-[(methyl) are preferred from the viewpoint of improving the solvent resistance of the obtained colored layer. Propylene methoxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane, 3-[(meth)acrylomethoxy group 2-fluoromethyl oxetane, 3-[(methyl) propylene methoxymethyl]-2-phenyl oxetane, 2-[(meth) propylene oxime Methyl]oxetane, 2-[(meth)acryloxymethyl]-4-trifluoromethyloxetane.

The compound (b1) may be used singly or in combination of two or more.

Further, examples of the compound (b2) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 5. -hydroxypentyl ester, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, ( a hydroxyalkyl (meth) acrylate such as 10-hydroxydecyl methacrylate, 11-hydroxyundecyl (meth) acrylate or 12-hydroxydodecyl (meth) acrylate; 2-(6-hydroxyhexyloxy)ethyl acrylate, 3-(6-hydroxyhexyloxy)propyl (meth)acrylate, 4-(6-hydroxyhexyloxy) (meth)acrylate (meth)acrylic acid (6) butyl ester, 5-(6-hydroxyhexyloxy)pentyl (meth)acrylate, 6-(6-hydroxyhexyloxy)hexyl (meth)acrylate, etc. -Hydroxyhexyloxy)alkyl ester and the like.

As a commercial product of a mixture of (6-hydroxyhexyloxy)alkyl methacrylate and 2-hydroxyethyl methacrylate, the trade name can be listed as PLACEL FM1D, FM2D (Dai Sil Chemical Industry Co., Ltd.) )Wait.

Further, 2-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl (meth)acrylate and 3-(3-hydroxy-2, (meth)acrylate may also be mentioned. 2-Dimethyl-propoxycarbonyloxy)-propyl ester, 4-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl (meth)acrylate, (A 5-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-pentyl acrylate, 6-(3-hydroxy-2,2-dimethyl-propyl (meth) acrylate (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl (meth)acrylate, etc., such as oxycarbonyloxy)-hexyl ester.

A commercially available product of a mixture of (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl (meth)acrylate and 2-hydroxyethyl methacrylate, and the trade name may be HEMAC1. (Dai Sil Chemical Industry Co., Ltd.) and so on.

Further, 4-hydroxy-cyclohexyl (meth)acrylate, 4-hydroxymethyl-cyclohexylmethyl (meth)acrylate, and 4-hydroxyethyl-cyclohexylethyl (meth)acrylate may also be mentioned. Ester, 3-hydroxy-bicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 3-hydroxymethyl-bicyclo[2.2.1]hept-5 -al-2-ylmethyl ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-en-2-ylethyl (meth)acrylate, 8-hydroxy-(meth)acrylate Bicyclo[2.2.1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methylene-indol-5-yl (meth)acrylate, (meth)acrylic acid 2-hydroxymethyl-octahydro-4,7-methylene-indol-5-ylmethyl ester, 2-hydroxyethyl-octahydro-4,7-methylene-indole-(meth)acrylate 5-ylethyl ester, 3-hydroxy-adamantan-1-yl (meth)acrylate, 3-hydroxymethyl-adamantan-1-ylmethyl (meth)acrylate, (meth)acrylic acid a hydroxyalkyl (meth) acrylate having an alicyclic structure such as 3-hydroxyethyl-adamantan-1-ylethyl ester; 1,2-dihydroxyethyl (meth)acrylate, (methyl) 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl (meth)acrylate, 3,4-dihydroxy (meth)acrylate Butyl ester, poly(hydroxy)alkyl (meth)acrylate such as 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl (meth)acrylate Ester and the like.

In the synthetic compound (b2) to which the precursor copolymer (1) is supplied, 2-hydroxyethyl (meth)acrylate is preferred from the viewpoints of copolymerization reactivity and reactivity with the compound (b3). , 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate, 2-(meth)acrylate (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl ester, 4-hydroxymethyl-cyclohexylmethyl (meth)acrylate, 3-hydroxymethyl (meth)acrylate Alkadamantan-1-ylmethyl ester, 2,3-dihydroxypropyl (meth)acrylate, and the like.

The compound (b2) may be used singly or in combination of two or more.

The above compound (b3) is a compound having an ethylenically unsaturated bond and an isocyanate group, and examples thereof include (meth)acryloxylated isocyanate, 2-(meth)acryloxyphenyl isocyanate, and 2-(p- Vinylphenyl)propan-2-yl isocyanate, 2-(meth)acryloxyethyl isocyanate, 3-(meth)acryloxypropyl isocyanate, 4-(methyl)propenyloxy Butyl isocyanate, 6-(meth) propylene methoxyhexyl isocyanate, 8-(meth) propylene decyl octyl isocyanate, 10-(meth) propylene decyl decyl isocyanate, 1, 1-[ Di(meth)acryloxymethyl]ethyl isocyanate, 1,1,1-[tris(meth)acryloxymethyl]methyl isocyanate, 2-(2-isocyanate) (meth)acrylate Ethyl ethoxy)ethyl ester, 2-[2-(2-isocyanatoethoxy)ethoxy]ethyl (meth)acrylate, 2-[2-[2-(2)(meth)acrylate -isocyanate ethoxy)ethoxy]ethoxy]ethyl ester, 2-(2-isocyanatopropyloxy)ethyl (meth)acrylate, 2-[2-(2) (meth)acrylic acid - Isocyanatopropoxy)propoxy]ethyl ester and the like.

In the compound (b3), a commercially available product of 2-propenyloxyethyl isocyanate may be exemplified by KARENS AOI (produced by Showa Denko Co., Ltd.) as 2-methylpropenyloxyethyl isocyanate. Commercially available products, such as KARENS MOI (produced by Showa Denko Co., Ltd.), are commercially available as 2-(2-isocyanate ethoxy)ethyl methacrylate, and the trade name can be listed as KARENS MOI- EG (produced by Showa Denko Electric Co., Ltd.), which is a commercial product of 1,1-(dipropenyloxymethyl)ethyl isocyanate, and the product name is KARENS BEI (produced by Showa Denko Co., Ltd.).

Among these compounds (b3), 2-(meth)acryloxyethyl isocyanate and 4-(meth)acryloxybutyl isocyanate are preferred from the viewpoint of reactivity with the compound (b2). 2-(2-Isocyanate-ethoxy)ethyl (meth)acrylate and 1,1-[bis(methyl)propenyloxymethyl]ethyl isocyanate.

In the synthesis of the polymer (B-1), the compound (b3) may be used singly or in combination of two or more.

Further, examples of the compound (b4) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. Unsaturated diacid or its anhydride such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, mesaconic anhydride; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, o-benzene Mono[(methyl)propenyloxyalkyl]ester of a divalent or higher polycarboxylic acid such as [2-(meth)acryloxyethyl) dicarboxylate; ω-carboxypolycaprolactone mono ( A mono(meth)acrylate or the like of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as a methyl acrylate.

When these compounds (b4) are used for the synthesis of the precursor copolymer (2), from the viewpoint of copolymerization reactivity and easy availability, (meth)acrylic acid, succinic acid mono [2-(methyl) is preferred. Propylene oxiranyl ethyl ester, ω carboxy polycaprolactone mono (meth) acrylate.

On the other hand, when the compound (b4) is used to react with the precursor copolymer (3) to synthesize the polymer (B-3), it is preferred from the viewpoints of reactivity with the compound (b5), availability, and the like. It is (meth)acrylic acid.

The compound (b4) may be used singly or in combination of two or more.

Further, examples of the compound (b5) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 3,4-epoxybutyl (meth)acrylate. 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ( Ethylene 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, etc. Ethyl (meth) acrylate; α-ethyl glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-ring Α-alkyl acrylate having an oxiranyl group such as oxyheptyl ester; 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane A vinyl compound having an oxirane group such as an alkane, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether.

Among these compounds (b5), in the case of the synthesis of the precursor copolymer (3) and the synthesis of the polymer (B-2) by reaction with the precursor copolymer (2), it is preferred to have a ring. The (meth) acrylate (meth) acrylate is preferably glycidyl (meth)acrylate or 2-methyl (meth)acrylate from the viewpoint of improving the development resistance and solvent resistance of the obtained colored layer. Glycidyl ester, 4-glycidyloxybutyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate.

The compound (b5) may be used singly or in combination of two or more.

Further, the compound (b6) is a polymerizable unsaturated compound other than the compounds (b1) to (b5) which can be copolymerized in the precursor copolymers (1) to (3). Specific examples thereof include: maleimide; N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N - p-hydroxyphenyl maleimide, N-benzyl maleimide, N-cyclohexylmaleimide, N-succinimide-3-maleimidobenzoic acid Ester, N-succinimide-4-maleimido butyrate, N-succinimide-6-maleimidohexanoate, N-ammonium imino group- N-substituted maleic imine such as 3-maleimide propionate or N-(acridinyl)maleimide; styrene, α-methylstyrene, o-vinyltoluene, M-vinyl toluene, p-vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol , an aromatic vinyl compound such as p-hydroxy-α-methylstyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether; terpene, 5-chlorodecene, Terpenes such as 5-hydroxymethyl decene and 5-hydroxy decene; hydrazine, 1-methyl Equivalent oxime; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth)acrylic acid alkyl ester such as isobutyl methacrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate; Cyclohexyl methyl methacrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate, isobornyl (meth) acrylate An alicyclic ester of (meth)acrylic acid such as an ester or a tetrahydrofurfuryl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxy benzene (meth) acrylate Ethyl (meth) acrylate such as ester; 2-methoxy (meth) acrylate, 2-phenoxyethyl (meth) acrylate, polyethylene glycol (n = 2 to 100) methyl ether (meth) acrylate, polypropylene glycol (n=2~100) methyl ether (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumyl phenol, etc. having an alkylene oxide structure (meth) acrylate; allyl (meth) acrylate; vinyl acetate, Vinyl carboxylate, vinyl butyrate, vinyl benzoate, etc.; unsaturated ether such as vinyl methyl ether or vinyl ethyl ether; (meth)acrylonitrile, α-chloroacrylonitrile, partial a vinyl cyanide compound such as vinyl cyanide; an unsaturated decylamine such as (meth) acrylamide, α-chloropropenylamine or N-2-hydroxyethyl(meth) acrylamide; Aliphatic conjugated diene such as olefin, isoprene or chloroprene; polymer molecules such as polystyrene, poly(methyl) acrylate, poly(meth) acrylate, polysiloxane A macromonomer having a mono(meth)acrylinyl group at the end of the chain or the like.

The compound (b6) may be used singly or in combination of two or more.

Further, the copolymer (b4) may be alkali-soluble in the precursor copolymer (1), and the compound (b2) may be copolymerized in the precursor copolymers (2) and (3).

In the present invention, as the compound (b6), a N-substituted maleimide, an aromatic vinyl compound, a terpene, an alkyl (meth)acrylate, or a (meth)acrylic acid is preferable. An alicyclic ester, an aryl (meth) acrylate, an allyl (meth) acrylate, a (meth) acrylate having an alkylene oxide structure, particularly preferably an N-phenyl maleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, terpene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylic acid of p-cumylphenol Ester, allyl (meth) acrylate.

The copolymerization ratio of the compound (b1) in the precursor copolymer (1) is usually 10 to 90% by weight, preferably 10 to 80% by weight. The copolymerization ratio of the compound (b2) in the precursor copolymer (1) is usually 5 to 90% by weight, preferably 10 to 80% by weight.

The copolymerization ratio of the compound (b1) in the precursor copolymer (2) is usually from 5 to 90% by weight, preferably from 10 to 80% by weight. The copolymerization ratio of the compound (b4) in the precursor copolymer (2) is usually 5 to 50% by weight, preferably 10 to 40% by weight.

The copolymerization ratio of the compound (b1) in the precursor copolymer (3) is usually 5 to 90% by weight, preferably 10 to 80% by weight. The copolymerization ratio of the compound (b5) in the precursor copolymer (3) is usually 5 to 90% by weight, preferably 10 to 80% by weight.

By synthesizing the copolymerization ratio of the compounds (b1) to (b5) within the above range when synthesizing the precursor copolymers (1) to (3), it is possible to synthesize a non-gelled polymer at a desired conversion ratio ( B-1) to (B-3) are preferable because the development resistance and solvent resistance of the radiation sensitive composition containing the obtained polymers (B-1) to (B-3) can be improved.

The precursor copolymers (1) to (3) can be, for example, each of the polymerizable unsaturated compounds in a suitable solvent in 2,2'-azobisisobutyronitrile, 2,2'-azobis ( Preparation by polymerization in the presence of a radical polymerization initiator such as 2,4-dimethylvaleronitrile or 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) .

The precursor copolymers (1) to (3) can be produced by subjecting the polymerizable unsaturated compound to radical polymerization as described above, followed by reprecipitation purification using two or more organic solvents having different polarities. In other words, the solution in the good solvent after the polymerization is removed by infiltration or centrifugation as necessary, and then a large amount of a precipitant (usually 5 to 10 times the volume of the polymer solution) is introduced (poor solvent). In the case, the copolymer is reprecipitated and refined. At this time, among the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified precursor copolymers (1) to (3).

As a combination of a good solvent/precipitant used in the reprecipitation method, for example, diethylene glycol monomethyl ether acetate/n-hexane, methyl ethyl ketone/n-hexane, diethylene glycol monomethyl ether acetate may be mentioned. / n-heptane, methyl ethyl ketone / n-heptane, and the like.

In addition, the precursor copolymers (1) to (3) can also be obtained by using each polymerizable unsaturated compound in 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-). Radical polymerization initiators such as dimethyl valeronitrile and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and pyrazole-1-dithiocarboxylic acid Cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethyl thiuram disulfide, bis(pyrazole-1-ylthiocarbonyl) disulfide , bis(3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(5-methyl- Pyrazol-1-ylthiocarbonyl)disulfide, bis(3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis(pyrrol-1-ylthiocarbonyl) In the presence of a molecular weight modifier such as disulfide or dithiobenzhydryl disulfide which initiates a transfer terminator, in an inert solvent, the reaction temperature is usually from 0 to 150 ° C, preferably 50 °. Prepared by living radical polymerization at 120 °C.

Further, the precursor copolymers (1) to (3) may be in a suitable solvent by using each of the polymerizable unsaturated compounds in the presence of the above-mentioned radical polymerization initiator and a polyvalent thiol compound acting as a chain transfer agent. Prepared by performing free radical polymerization. Here, the polythiol compound refers to a compound having two or more mercapto groups in one molecule, and examples thereof include trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate). Tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), 1,4-bis(3-mercaptobutyloxy) Butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione and the like.

The synthesis of the polymer (B-1), that is, the reaction of the hydroxyl group possessed by the precursor copolymer (1) with the compound (b3), can be carried out by a catalyst containing a precursor copolymer (1), if necessary, in a catalyst and polymerization. In the presence of a blocking agent, the method of adding the compound (b3) to carry out the reaction is carried out. As the solution containing the precursor copolymer (1), the polymer solution in the case of synthesizing the precursor copolymer (1) may be used as it is, or the precursor copolymer (1) may be separated from the polymer solution and dissolved. In another solvent.

The amount of the compound (b3) to be used is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%, based on the total amount of the hydroxyl groups of the precursor copolymer (1). When the amount of the compound (b3) used is too small, the desired effect cannot be obtained. On the other hand, if too much, unreacted compound (b3) remains in the reaction solution, and the resulting polymer solution and radiation are obtained. There is a danger that the storage stability of the sexual composition will decrease.

As the catalyst, a catalyst such as di-n-butyltin dilaurate (IV) can be used. Further, examples of the polymerization inhibitor include p-methoxyphenol, p-benzoquinone, and phenothiazine. Wait. The preferred reaction conditions are: a temperature of 20 to 100 ° C and a reaction time of 1 to 10 hours.

The synthesis of the polymer (B-2), that is, the reaction of the carboxyl group possessed by the precursor copolymer (2) with the compound (b5), except that the precursor copolymer (2) is used in place of the precursor copolymer (1), respectively. The compound (b5) may be used in place of the compound (b3) in addition to the synthesis of the above polymer (B-1). The amount of the compound (b5) to be used is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%, based on the total amount of the carboxyl groups of the precursor copolymer (2). As the catalyst, tetrabutylammonium bromide or triethylamine can be used.

When the polymer (B-2) is synthesized, the polymer (B-2) can be made alkali-soluble by adjusting the amount of the compound (b5) to leave an unreacted carboxyl group.

The synthesis of the polymer (B-3), that is, the reaction of the oxirane group of the precursor copolymer (3) with the compound (b4), except that the precursor copolymer (3) is used instead of the precursor copolymer ( 1) and the compound (b4) may be used in place of the compound (b3) in accordance with the synthesis of the above polymer (B-1). The amount of the compound (b4) to be used is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%, based on the total amount of the oxirane groups of the precursor copolymer (3). As the catalyst, the same catalyst as used in the synthesis of the polymer (B-2) can be used.

In the present invention, the polymer (B) may be used singly or in combination of two or more.

In the present invention, the content of the polymer (B) is usually 5 to 800 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the (A) coloring agent. If the content of the polymer (B) is too small, there is a possibility that the desired effect cannot be obtained. On the other hand, if the amount is too large, since the pigment concentration is relatively small, there is a risk that the film hardly reaches the target color density.

-(C) Photopolymerization Initiator -

The (C) photopolymerization initiator in the present invention means that the above polymer (B) can be produced and used as needed by exposure using radiation containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. (D) a compound of a polymerized active species of a monomer having a polymerizable unsaturated bond.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a diimidazole compound, and the like. Compounds, O-mercaptopurines, phosphonium salts, benzoin compounds, benzophenones, α-diketones, polynuclear terpenoids, diazo compounds, sulfhydrazine sulfonic acid An ester (imide sulfonate) compound or the like.

In the present invention, the photopolymerization initiators may be used singly or in combination of two or more. The photopolymerization initiator preferably contains a compound selected from the group consisting of thioxanthone compounds, acetophenone compounds, diimidazole compounds, and three At least one of the group consisting of a compound or an O-mercaptoquinone compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the above acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzimidyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, specific examples of the above diimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole. 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-di(2,4, 6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like.

Further, when a diimidazole compound is used as the photopolymerization initiator, it is preferably used in combination with a hydrogen donor from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated by a diimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, and 4,4. An amine hydrogen donor such as '-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. It is preferred to combine one or more thiol hydrogen donors with one or more amine hydrogen donors from the viewpoint of further improving the sensitivity. use.

In addition, as the above three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-di(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-di(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-di(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-di(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-di(trichloromethyl)-s-three 2-(4-methoxyphenyl)-4,6-di(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-di(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-di(trichloromethyl)-s-three Three with a halogenated methyl group Class of compounds.

Further, as a specific example of the O-indenyl quinone compound, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidenefluorene) can be cited. Ethylketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene]- 9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like.

In the present invention, when a photopolymerization initiator other than a diimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethylamino group can be mentioned. Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-di(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the polymer (B). When the content of the photopolymerization initiator is too small, there is a risk that exposure curing is insufficient. On the other hand, if the amount is too large, the formed coloring layer tends to fall off from the substrate during development.

- (D) monomer having a polymerizable unsaturated bond -

In the present invention, the sensitivity of the radiation sensitive composition can be improved by further using (D) a monomer having a polymerizable unsaturated bond. Examples of the monomer having a polymerizable unsaturated bond include a polyfunctional monomer having two or more polymerizable unsaturated bonds, and a monofunctional monomer having one polymerizable unsaturated bond.

Examples of the polyfunctional monomer include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and di(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Poly(meth)acrylates of dihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol or the like thereof; polyesters, epoxy resins, polyamines Oligomeric (meth) acrylates such as acid ester resins, alkyd resins, polyoxyxylene resins, and spiro resins; hydroxy poly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, a di(meth)acrylate of a two-terminal hydroxyl polymer such as a hydroxypolycaprolactone at both ends; or a tris[2-(methyl)propenyloxyethyl]phosphate or an isocyanuric acid ethylene A triacrylate; a poly(meth)acrylate having a urethane structure; and the like.

These polyfunctional monomers may be used singly or in combination of two or more.

Further, examples of the monofunctional monomer include succinic acid mono [2-(methyl) propylene methoxyethyl] ester, and phthalic acid mono [2-(methyl) propylene methoxyethyl group. a mono[(meth)acryloxyalkylene] ester of a divalent or higher polycarboxylic acid such as an ester; a polymer having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate Mono (meth) acrylate; N-vinyl succinimide, N-vinyl pyrrolidone, N-vinyl phthalimide, N-vinyl-2-acridone, N-ethylene Base-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazoline, N-vinylfluorene, N-vinylporphyrin, N-vinylbenzimidazole, N-vinylcarbazole, N-vinyl acridine, N-vinyl anthracene N-vinyl Porphyrin, N-vinyl pheno N-vinyl nitrogen-containing heterocyclic compound; N-(methyl) propylene fluorenyl In addition, as a commercial item, M-5400, M-5600 (brand name, the production of East Asia synthesis), etc. are mentioned.

These monofunctional monomers may be used singly or in combination of two or more.

In the present invention, as the monomer having a polymerizable unsaturated bond, a polyfunctional monomer, preferably a poly(meth)acrylate of a trihydric or higher polyhydric alcohol, and a dicarboxylic acid modification thereof are preferred. And poly(meth) acrylate having a urethane structure. As the poly(meth) acrylate of a trihydric or higher polyhydric alcohol and a dicarboxylic acid modified product thereof, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol are preferable. Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, a monoester of pentaerythritol triacrylate and succinic acid, a monoester of pentaerythritol trimethacrylate and succinic acid, a monoester of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol penta methacrylate and succinic acid The monoester compound is excellent in strength from the colored layer, excellent in surface smoothness of the colored layer, and it is difficult to generate scum, residual film, etc. on the unexposed portion of the substrate and the light shielding layer, and is particularly preferably trimethylolpropane triacrylate. Ester, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Acrylate and succinic acid monoester and dipentaerythritol pentaacrylate succinic acid monoester with.

The content of the monomer having a polymerizable unsaturated bond in the present invention is preferably from 1 to 500 parts by weight, more preferably from 5 to 300 parts by weight, per 100 parts by weight of the polymer (B). By making the monomer having a polymerizable unsaturated bond in such a ratio, a more sensitive radiation sensitive composition can be obtained.

- (E) alkali soluble resin -

In the present invention, by further using (E) an alkali-soluble resin (excluding the component (B)), developability and storage stability of the obtained radiation sensitive composition can be improved. The alkali-soluble resin is not particularly limited as long as it functions as a binder for the (A) colorant and is soluble in the alkaline developer used in the development treatment step, and usually has a carboxyl group, a phenolic hydroxyl group, or the like. A polymer of an acidic functional group. In particular, a polymer having a carboxyl group is preferable. Specific examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "carboxyl-containing unsaturated monomer") and other copolymerizable ones. A copolymer of an ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (e)") (hereinafter also referred to as "polymer (E1)").

Specific examples of the carboxyl group-containing unsaturated monomer include compounds exemplified as the compound (b4) in the polymer (B).

In the present invention, as the carboxyl group-containing unsaturated monomer, (meth)acrylic acid, succinic acid mono [2-(methyl)propenyloxyethyl]ester, and ω-carboxypolycaprolactone mono ( Methyl) acrylate or the like is particularly preferably (meth)acrylic acid.

These carboxyl group-containing unsaturated monomers may be used singly or in combination of two or more.

In the polymer (E1), the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the copolymerization ratio is too small, the solubility of the obtained radiation sensitive composition tends to be small in the alkaline developing solution. On the other hand, if the amount is too large, the solubility in the alkaline developing solution is too large, and alkaline is used. When the developer is developed, it tends to cause the pixels to fall off from the substrate and the film surface to crack.

Further, specific examples of the unsaturated monomer (e) include compounds exemplified as the compound (b2) and the compound (b6) in the polymer (B).

In the present invention, as the unsaturated monomer (e), a compound (b2), an N-substituted maleimide, an aromatic vinyl compound, a terpene, or an alkyl (meth)acrylate is preferred. , an alicyclic ester of (meth)acrylic acid, an aryl (meth)acrylate, a (meth) acrylate having an alkylene oxide structure, and a large (meth)acryl fluorenyl group at the end of the polymer molecular chain Molecular monomer, particularly preferably N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, terpene, Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol, Polystyrene macromonomer, polymethyl methacrylate macromonomer.

These unsaturated monomers (e) may be used singly or in combination of two or more.

In the present invention, a carboxyl group having a polymerizable unsaturated bond such as a (meth)acryl fluorenyl group in a side chain disclosed in JP-A No. Hei 6-230212, or the like, which is disclosed in JP-A No. Hei. A copolymer or a polymer having a repeating unit represented by the following formula (I) (hereinafter referred to as "polymer (E2)") is used as an alkali-soluble resin.

(wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a monovalent organic group having a propylene fluorenyl group or a methacryl fluorenyl group or ethylene; A group or a 1-methylvinyl group, Y represents a divalent organic group, and i represents an integer of 1 to 5).

In the above formula (1), R ^{1 is} preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ² and R ^{3 are} preferably a hydrogen atom. i is preferably 1.

In the above formula (1), the monovalent organic group having an acrylonitrile group or a methacryloyl group as X is preferably represented by the following formula (X-1) or the following formula (X-2). Group. As X in the above formula (I), a vinyl group or a 1-methylvinyl group is preferred.

(wherein R ⁴ represents a hydrogen atom or a methyl group, j represents an integer of 0 to 10, and "*" represents a linkage).

(wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a cyclohexane-1,2-diyl group or a 1,2- Stretch phenyl, "*" means the connection key).

The Y in the above formula (I) is preferably a methylene group, an alkylene group having 2 to 6 carbon atoms or an alkenyl group (wherein the alkyl group and the alkenyl group may have an ether bond), and a ring. a hexanediyl group, a cyclohexenediyl group, or an arylene group having 6 to 12 carbon atoms (wherein the arylene group may further have a carboxyl group or an acid anhydride group), more preferably a methylene group, an ethyl group, and 1 , 3-propyl, 1,2-vinylidene, 1,2-propylene, 1,3-propylene, 2,3-propylene, cyclohexane-1,2-diyl, a divalent group represented by 4-cyclohexene-1,2-diyl, 1,2-phenylene, biphenyl-2,2'-diyl or -CH ₂ -O-CH ₂ -.

In the polymer (E2), the repeating unit represented by the above formula (I) is preferably 5 to 80% by weight, more preferably 10 to 60% by weight based on the total repeating unit of the polymer (E2). When the number of repeating units represented by the above formula (I) is too small, the solubility of the obtained radiation sensitive composition tends to be small in the alkaline developing solution. On the other hand, if the amount is too large, the solubility in the alkaline developing solution is too large. When developing with an alkaline developer, it tends to cause the pixels to fall off from the substrate and the film surface to crack.

In the polymer (E2), it is preferred to further have the same unsaturated monomer as the unsaturated monomer (e) exemplified for the polymer (E1) together with the repeating unit represented by the above formula (I). Repeat unit.

The Mw of the alkali-soluble resin in the present invention is preferably from 1,000 to 45,000, particularly preferably from 3,000 to 30,000. Further, the ratio (Mw/Mn) of Mw to Mn of the alkali-soluble resin in the present invention is preferably from 1 to 5, more preferably from 1 to 4. When the Mw is too small, the residual film ratio of the obtained film is lowered, and the pattern shape, heat resistance, and the like are impaired, and the electrical properties are deteriorated. On the other hand, if the Mw is too large, the resolution is lowered to impair the pattern shape. Moreover, the risk of drying foreign matter is likely to occur when coating is performed using the slit nozzle method.

The polymer (E1) can be produced in the same manner as the above precursor copolymers (1) to (3).

The polymer (E2) can be, for example, a vinylbenzyl (poly)glycidyl ether such as p-vinylbenzyl glycidyl ether or the above unsaturated monomer, which is the same as the above-mentioned precursor copolymers (1) to (3). Copolymerization, addition of acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, on the glycidyl group in the obtained copolymer, 2 - an unsaturated carboxylic acid such as acryloxyethyl succinate or 2-methylpropenyloxyethyl succinate, followed by addition of succinic anhydride, glutaric anhydride, phthalic anhydride, 4-cyclohexane It is prepared by using a polycarboxylic acid anhydride such as an ene-1,2-dicarboxylic anhydride. The addition reaction of the unsaturated carboxylic acid and the polycarboxylic acid anhydride can be carried out in accordance with a known method.

In the present invention, the alkali-soluble resins may be used singly or in combination of two or more.

In the present invention, the content of the alkali-soluble resin is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, per 100 parts by weight of the (A) coloring agent. By containing an alkali-soluble resin in such a ratio, a radiation-sensitive composition excellent in developability and storage stability can be obtained.

-additive-

The radiation sensitive composition of the present invention may further contain various additives as needed.

As the additive, a thermal acid generator which promotes an oxiranyl group ring-opening hardening reaction which the polymer (B) has in the post-baking step can be mentioned. Examples of the thermal acid generator include an onium salt, a benzothiazolium salt, an ammonium salt, a phosphonium salt, a sulfonate compound, a sulfoximine compound, and a diazomethane compound. Among them, an onium salt, a benzothiazolium, a sulfonate compound, a sulfoximine compound, and a diazomethane compound are preferable.

Preferred examples of the thermal acid generator include 4-ethyloxy phenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, and 4-ethyl hydrazine. Oxyphenylbenzylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, 4-acetoxyphenylbenzylphosphonium hexafluoroantimonate, 3-benzyl Benzothiathiazolidine hexafluoroantimonate, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid quinone imine, and the like.

Examples of other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, and anionic surfaces. Surfactant such as active agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propoxypropyltrimethoxydecane, 3-glycidoxymethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Adhesion promoters such as methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2 Antioxidants such as thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-t-butylphenol; 2-(3-tert-butyl-5-methyl-2- UV, such as hydroxyphenyl)-5-chlorobenzothiazole and alkoxybenzophenone Line absorber; anticoagulant such as sodium polyacrylate.

- solvent -

The radiation sensitive composition of the present invention contains the above components (A) to (C) and optionally other components, and is usually prepared by mixing a solvent to prepare a liquid composition.

The solvent can be appropriately selected as long as it can disperse or dissolve the components (A) to (C) constituting the radiation sensitive composition and other components, and does not react with these components and has appropriate volatility. .

Examples of such a solvent include alcohols such as methanol, ethanol, and benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and digan. Alcohol 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, two Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly) alkanediol monoalkyl ether; ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, digan Alcohol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl (poly)alkylene glycol monoalkyl ether acetates such as acetoxyacetate; diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers ; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexene- Ketones such as 2-ketone; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate; methyl lactate, ethyl lactate, etc. Alkyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, 3-methoxybutyl B Acid ester, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-butyrate Ester, isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-hydroxy-2- Other esters such as ethyl methacrylate, methyl 2-hydroxy-3-methylbutanoate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N- Pyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide and the like Amides.

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Ester, ethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diglyme, diethylene glycol Ethyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate, 1,3-butanediol diacetate, n-butyl acetate, isobutyl acetate, n-pentyl formate Ester, isoamyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl pyruvate, and the like.

The above solvents may be used singly or in combination of two or more.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, benzene may be used together with the above solvent. A high boiling point solvent such as ethyl formate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate.

The above high boiling point solvents may be used singly or in combination of two or more.

Color filter

The color filter of the present invention has a coloring layer formed of the radiation sensitive composition of the present invention.

Hereinafter, a method of forming the color filter of the present invention will be described.

First, on the surface of the substrate, a light-shielding layer (black matrix) in which a pixel portion is to be formed is formed as needed, and then a liquid composition in which a radiation-sensitive linear composition such as a red pigment is dispersed is applied onto the substrate, Prebaking is carried out to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film, followed by post-baking to form a pixel array in which a red pixel pattern was arranged in a predetermined layout.

Then, the liquid composition of each of the radiation-sensitive linear compositions in which the green or blue pigment is dispersed is applied, and the coating, prebaking, exposure, development, and post-baking of the respective liquid compositions are carried out in the same manner as described above, and sequentially formed on the same substrate. A green pixel array and a blue pixel array are used to produce a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on a substrate. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above order.

Further, as the black matrix, the radiation sensitive composition of the present invention can be used in the same manner as in the case of forming the above-described pixels.

Examples of the substrate used in forming the pixel and/or the black matrix include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimine, and the like.

Further, these substrates may be subjected to chemical treatment such as decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum vapor deposition, or the like, as appropriate, in advance.

As a method of forming the coating film of the radiation sensitive composition of the present invention, for example, (1) coating method and (2) dry film method can be used.

When the (1) coating method is used, it is preferred that the radiation-sensitive composition of the present invention is applied onto a substrate as a composition solution, and then the coated surface is pre-baked to form a coating film.

As a coating method of the composition solution, for example, a suitable coating method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet coating method can be used. Coating method, slot die coating method.

The prebaking conditions vary depending on the type of each component, the blending ratio, etc., and are preferably from 1 to 15 minutes at 70 to 120 °C.

Further, in forming the coating film of the radiation sensitive composition of the present invention, when the (2) dry film method is used, the dry film is laminated on the base film, preferably the plastic base film, and is composed of the radiation sensitive composition of the present invention. It is formed by a radiation sensitive layer (hereinafter referred to as "radial radiation dry film").

The radiation sensitive dry film can be formed by applying a radiation sensitive layer of the present invention in a state in which the radiation sensitive composition of the present invention is preferably applied to the base film in a solution composition. As the base film of the radiation-sensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the base film is preferably in the range of 15 to 125 μm. The thickness of the obtained radiation sensitive layer is preferably about 1 to 30 μm. The removal of the solvent is preferably carried out by heating at 80 to 150 ° C for 1 to 10 minutes.

Further, when the radiation sensitive dry film is not used, the film may be further laminated on the radiation sensitive layer and stored. The film needs to have a moderate release property so that it does not fall off when not in use, and can be easily peeled off during use. As the film which satisfies such a condition, for example, a film of a polysiloxane-based release agent coated or sintered on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film or a polyvinyl chloride film can be used. It is sufficient that the thickness of the film is usually about 25 μm.

When the radiation sensitive composition of the present invention is used in a solution state, the solid content concentration (ratio of the weight after removing the solvent from the composition to the total weight of the composition) is preferably from 5 to 80% by weight. More preferably, the solid content concentration differs depending on the method of forming the film. When the coating method is used for the formation of the film, the solid content concentration is preferably 5 to 50% by weight, and when the film is formed by the dry film method, the solid content concentration is preferably 50 to 70% by weight.

The coating thickness, as a thickness after drying, is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, and particularly preferably 0.2 to 6.0 μm.

As the radiation used for forming the pixels and/or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. The exposure amount of the radiation is preferably 10 to 10000 J/m ² . The conventional radiation-sensitive composition is formed to have sufficient solvent resistance as disclosed in the examples of JP-A-2002-296778, JP-A-2007-316485, and JP-A-2007-316506. The pattern requires an exposure of 1500 to 2000 J/m ² . On the other hand, when the radiation sensitive composition of the present invention is used, a fine pattern having excellent development resistance and solvent resistance can be formed even when the exposure amount is 500 J/m ² or less.

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo[5.4.0]-7 is preferable. An aqueous solution of undecene, 1,5-diazabicyclo[4.3.0]-5-nonene or the like.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developing solution. Further, after alkali development, it is usually washed with water.

As the development treatment method, a rinse development method, a spray development method, a immersion (immersion) development method, a paste type (liquid) development method, or the like can be used. The developing conditions are preferably developed at room temperature for 5 to 300 seconds.

The color filter of the present invention thus obtained is valuable for high-definition color liquid crystal display elements, color photographic tube elements, color sensors, and the like.

Color liquid crystal display element

The color liquid crystal display element of the present invention has the color filter of the present invention.

The color liquid crystal display element of the present invention can take an appropriate configuration. For example, a color filter may be formed on a substrate other than the driving substrate on which the thin film transistor (TFT) is provided, and the driving substrate and the substrate on which the color filter is formed may face the liquid crystal layer, and A substrate in which a color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is provided and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be employed, and the liquid crystal layer may face each other. The latter configuration can significantly increase the aperture ratio, and has the advantage of being able to produce a bright, high-definition liquid crystal display element.

(Example)

Hereinafter, embodiments of the present invention will be more specifically described by way of examples. However, the invention is not limited to the following embodiments.

(modulation of pigment dispersion)

Modulation example 1

15 parts by weight of CI Pigment Red 254 (manufactured by Ciba Specialty Chemicals, trade name BK-CF), 4 parts by weight of Disperbyk-2000 (as solid content) as a dispersant, and a solvent were used as the solvent (A). A mixture of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 80 / 20 (by weight) was made to have a solid content concentration of 19%, which was treated with a ball mill to prepare a pigment dispersion liquid (A-1).

Modulation example 2

20 parts by weight of carbon black as (A) colorant, 4 parts by weight of Disperbyk-167 (in terms of solid content) as a dispersing agent, and 3-methoxybutyl acetate as a solvent were used to make a solid content concentration At 24%, it was treated with a ball mill to prepare a pigment dispersion (A-2).

Modulation example 3

15 parts by weight of CI Pigment Green 58 (produced by Dainippon Ink and Chemicals Co., Ltd.) / CI Pigment Yellow 150 = 60/40 (by weight) as a (A) coloring agent, and 4 parts by weight of Disperbyk as a dispersing agent. a mixture of -2001 (converted to solid content), propylene glycol monomethyl ether acetate / 1,3-butanediol diacetate = 50/50 (by weight) as a solvent, and having a solid content concentration of 19% It was treated with a ball mill, mixed with a ball mill, and dispersed for 12 hours to prepare a pigment dispersion liquid (A-3).

Modulation example 4

Using a mixture of 15 parts by weight of CI Pigment Green 36/CI Pigment Yellow 150=60/40 (weight ratio) as the (A) colorant, 4.0 parts by weight of Disperbyk-2001 (in terms of solid content) as a dispersing agent, as a solvent a mixture of propylene glycol monomethyl ether acetate/1,3-butanediol diacetate = 50/50 (by weight) to a solids concentration of 19%, treated with a ball mill, mixed with a ball mill, dispersed 12 The pigment dispersion (A-4) was prepared in an hour.

(Synthesis of precursor copolymer and polymer (B))

Synthesis of precursor copolymer

Synthesis Example 1

In a flask equipped with a condenser and a stirrer, 70.0 g of 3-propenyloxymethyl-3-ethyloxetane, 15.0 g of acrylic acid and 15.0 g of ω-carboxypolycaprolactone monoacrylate were dissolved. To 300 g of propylene glycol monomethyl ether acetate, 3.0 g of 2,2'-azobisisobutyronitrile and 5.0 g of α-methylstyrene dimer were further added, followed by purging with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C for 5 hours to obtain a solution containing 25% by weight of the precursor copolymer [b-1]. The polystyrene-equivalent weight average molecular weight (Mw) of the precursor copolymer [b-1] was 10,000.

Synthesis Example 2~9

The types and amounts of the compound (b1), the compound (b2), the compound (b4) and the compound (b6), the polymerization initiator, the chain transfer agent, and the molecular weight modifier which are the polymerizable unsaturated compounds are as shown in Table 1. In the same manner as in the above Synthesis Example 1, a solution containing 25% by weight of the precursor copolymers [b-2] to [b-9] was obtained.

The polystyrene-equivalent weight average molecular weight (Mw) of the precursor copolymer obtained in each Synthesis Example is shown in Table 1.

Synthesis of polymer (B)

Synthesis Example 10

200 g of the solution containing the precursor copolymer [b-1] obtained in the above Synthesis Example 1, 25.6 g of glycidyl methacrylate as the compound (b5), and 4-methoxyphenol as a polymerization inhibitor 0.2 g and 2.5 g of tetrabutylammonium bromide as a catalyst were placed in a flask, and reacted at 110 ° C for 9 hours. The reaction solution was washed with water for four times with 75 g of ion-exchanged water each time, and concentrated under reduced pressure to obtain a solution containing 33% by weight of the polymer [B-1]. The polymer [B-1] had a polystyrene-equivalent weight average molecular weight (Mw) of 1,1,500, an oxetanyl group content of 2.8 mmol/g, and a polymerizable unsaturated bond content of 1.8 mmol. /g.

Synthesis Example 11~14

The same procedure as in the above Synthesis Example 10 was carried out except that the type of the precursor copolymer used, the type of the compound (b5), the catalyst, and the polymerization inhibitor were as shown in Table 2, and 33% by weight of the polymer was obtained, respectively. -2]~[B-5] solution.

The polystyrene-equivalent weight average molecular weight (Mw), the content of the oxetane group, and the content of the polymerizable unsaturated bond of the polymer (B) obtained in each Synthesis Example are shown in Table 2.

Synthesis Example 15

200 g of the solution containing the precursor copolymer [b-6] obtained in the above Synthesis Example 6 and 47.6 g of 2-methylpropenyloxyethyl isocyanate as the compound (b3), as a polymerization inhibitor 4- 0.2 g of methoxyphenol was added to the flask, and the mixture was reacted at 110 ° C for 9 hours. The reaction solution was washed with water twice with 75 g of ion-exchanged water, and concentrated under reduced pressure to obtain a solution containing 33% by weight of the polymer [B-6]. The polymer [B-6] had a polystyrene-equivalent weight average molecular weight (Mw) of 13,600, an oxetanyl group content of 1.6 mmol/g, and a polymerizable unsaturated bond content of 3.1 mmol. /g.

Synthesis Example 16~18

The same procedure as in the above Synthesis Example 15 was carried out except that the type of the precursor copolymer used, the kind of the compound (b3) and the polymerization inhibitor, and the amounts thereof were as shown in Table 2, and 33% by weight of the polymer were respectively obtained [B-7 ]~[B-9] solution.

The polystyrene-equivalent weight average molecular weight (Mw), the content of the oxetane group, and the content of the polymerizable unsaturated bond of the polymer (B) obtained in each Synthesis Example are shown in Table 2.

Synthesis Example 19

In a flask equipped with a condenser and a stirrer, 55.0 g of 3-methacryloxymethyl-3-ethyloxetane, 15.0 g of methacrylic acid and 30.0 g of allyl methacrylate were used. The ester was dissolved in 200 g of propylene glycol monomethyl ether acetate, followed by 3.0 g of 2,2'-azobisisobutyronitrile and 4.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile). Then, it was purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction mixture was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C, and the temperature was maintained for 5 hours to obtain a solution containing 33% by weight of the polymer [B-10]. The polymer [B-10] had a polystyrene-equivalent weight average molecular weight (Mw) of 11,000, an oxetane group content of 2.8 mmol/g, and a polymerizable unsaturated bond content of 2.2 mmol. Ear / g.

((E) Synthesis of alkali-soluble resin)

Synthesis Example 20

In a flask equipped with a condenser and a stirrer, 20.0 g of methacrylic acid, 15.0 g of 2-hydroxyethyl methacrylate, 15.0 g of N-phenylmaleimide, 12.0 g of styrene, 10.0 g Benzyl methacrylate and 28.0 g of 2-ethylhexyl methacrylate were dissolved in 200 g of propylene glycol monomethyl ether acetate, and then 3.0 g of 2,2'-azobisisobutyronitrile and 5.0 g of α- were added. The methyl styrene dimer was then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction liquid was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C, and the temperature was maintained for 5 hours to obtain a solution containing 33% by weight of the alkali-soluble resin [E-1]. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin [E-1] was 11,000.

Synthesis Example 21

In a flask equipped with a condenser and a stirrer, 20.0 g of methacrylic acid, 25.0 g of N-phenylmaleimide, 15.0 g of styrene, 5.0 g of benzyl methacrylate, and 15.0 g of methacrylic acid were used. 2-hydroxyethyl ester and 20.0 g of allyl methacrylate were dissolved in 200 g of propylene glycol monomethyl ether acetate, and then 7.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. And 7.0 g of α-methylstyrene dimer, then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction liquid was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C, and the temperature was maintained for 5 hours to obtain a solution containing 33% by weight of the alkali-soluble resin [E-2]. The alkali-soluble resin [E-2] had a polystyrene-equivalent weight average molecular weight (Mw) of 10,000.

Synthesis Example 22

In a flask equipped with a condenser and a stirrer, 15.0 g of methacrylic acid, 30.0 g of decene, 35.0 g of benzyl methacrylate, and 20.0 g of glycerol monomethacrylate were dissolved in 200 g of propylene glycol monomethyl ether acetate. To the ester, 4.0 g of 2,2'-azobisisobutyronitrile and 6.0 g of α-methylstyrene dimer were further added, followed by purging with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C, and the temperature was maintained for 5 hours to obtain a solution containing 33% by weight of the alkali-soluble resin [E-3]. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin [E-3] was 13,000.

Synthesis Example 23

In a flask equipped with a condenser and a stirrer, 44.0 g of p-vinylbenzyl glycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of benzyl methacrylate were dissolved in 300 g of propylene glycol. In methyl ether acetate, 8.0 g of 2,2'-azobisisobutyronitrile and 8.0 g of α-methylstyrene dimer were further added, followed by purging with nitrogen for 15 minutes. After purging with nitrogen, the reaction mixture was stirred and nitrogen gas was bubbled, and the mixture was heated at 80 ° C for 5 hours.

Then, 17.0 g of methacrylic acid, 0.5 g of p-methoxyphenol, and 4.4 g of tetrabutylammonium bromide were added to the reaction solution, and the mixture was reacted at 120 ° C for 9 hours. Further, 18.5 g of succinic anhydride was added, and the mixture was reacted at 100 ° C for 6 hours, and then washed twice with water while maintaining the liquid temperature at 85 ° C, and concentrated under reduced pressure to obtain 33% by weight of alkali-soluble. A solution of the resin [E-4]. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin [E-4] was 7,800.

Comparative synthesis

Synthesis Example 24

200 g of the solution containing the soluble resin [E-1] obtained in the above Synthesis Example 20, 12.8 g of glycidyl methacrylate as the compound (b5), 0.2 g of 4-methoxyphenol as a polymerization inhibitor, and 2.0 g of tetrabutylammonium bromide as a catalyst was placed in a flask, and reacted at 110 ° C for 9 hours. The reaction solution was washed with water 75 times each time with 75 g of ion-exchanged water, and concentrated under reduced pressure to obtain a solution containing 33% by weight of the polymer [R-1]. The polystyrene-equivalent weight average molecular weight (Mw) of the polymer [R-1] was 12,500.

Modulation and evaluation of radiation sensitive linear compositions Example 1

Modulation of radioactive linear composition

100.0 parts by weight of the pigment dispersion liquid (A-1) as the coloring agent (A), and 40.0 parts by weight of a solution (solid content concentration: 33%) of the polymer (B-1) containing the polymer (B) as (C) IRGACURE 907 (2-methyl-1-[4-(methylthio)phenyl]-2-) manufactured by Ciba Specialty Chemicals Co., Ltd. 5.4 parts by weight of M-402 (dipentaerythritol hexaacrylate) produced by Toagosei Co., Ltd. as a monomer having (D) a monomer having a polymerizable unsaturated bond, and a compound of East Asia Synthetic Co., Ltd. TO-1382 (a mixture of dipentaerythritol pentaacrylate and succinic acid monoester, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) produced by the company, 3.6 parts by weight, as an alkali-soluble resin of (E) alkali-soluble resin [E-1] 10.0 parts by weight and 4.0 parts by weight of an alkali-soluble resin [E-4] and 81.0 parts by weight of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a composition for forming a colored layer.

The obtained radiation sensitive composition was evaluated in the following order. The evaluation results are shown in Table 3.

Pattern formation

The obtained radiation sensitive composition was applied onto a soda lime glass substrate having a SiO ₂ film on the surface where sodium ions were prevented from eluting using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness of 1.7 μm coating film.

Then, after the substrate was cooled to room temperature, the coating film was irradiated at 365 nm and 405 nm with an illuminance of 40 mW/cm ² by using a high-pressure mercury lamp with a plurality of slit masks having different sizes ranging from 5 to 50 μm. And UV exposure at 436 nm wavelengths. The exposure amount at this time was 500 J/m ² . Then, the substrate was washed with a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C for 1 minute, and then washed with ultrapure water and dried. Then, post-baking was performed in a clean oven at 220 ° C for 30 minutes to form a pixel array having a red striped pixel pattern on the substrate.

Residue evaluation

The substrate obtained in the formation of the above pattern was observed, and whether or not the residue remained in the unexposed portion was evaluated in accordance with the following three grades.

○: No residue was identified

△: A small amount of residue was identified

×: A large amount of residue was identified

Evaluation of development resistance

In the formation of the above-mentioned pattern, when the thickness ratio (film thickness after development/film thickness before development) of the pixel pattern having a width of 50 μm is 95% or more, it is evaluated as ○, and the film thickness before and after development When the ratio was less than 95%, or when a part of the dot pattern was identified as a defect, it was evaluated as Δ, and when the pattern was all detached from the substrate after development, it was evaluated as ×.

Evaluation of voltage retention

The obtained radiation-sensitive composition was coated on a surface with a spin coater to form a SiO ₂ film for preventing elution of sodium ions, and a soda lime glass in which an ITO (indium-tin oxide alloy) electrode was vapor-deposited in a predetermined shape. After the substrate was placed, it was prebaked in a clean oven at 90 ° C for 10 minutes to form a coating film having a film thickness of 1.8 μm.

Then, using a high-pressure mercury lamp, exposure of radiation having wavelengths of 365 nm, 405 nm, and 436 nm was performed on the coating film at an exposure amount of 500 J/m ² without using a photomask. Then, the substrate was immersed in a developing solution composed of a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C for 1 minute for development, washed with ultrapure water and air-dried, and then baked at 230 ° C for 30 minutes to be coated. The film is cured to form a red pixel on the substrate.

Then, the liquid crystal cell was placed in a constant temperature layer of 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured using a liquid crystal voltage retention ratio measurement system VHR-1A (trade name) manufactured by Toyo Technica. The voltage applied at this time was a square wave of 5.0 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value (a liquid crystal cell potential difference after 16.7 milliseconds / a voltage applied at 0 milliseconds). The evaluation results are shown in Table 3.

Solvent resistance evaluation

The substrate obtained by the formation of the above pattern was immersed in N-methylpyrrolidone at 60 ° C for 30 minutes, and as a result, the thickness ratio (film thickness after immersion/film thickness before immersion) before and after immersion was 95% or more and 100%. When the immersion N-methylpyrrolidone is completely uncolored, it is evaluated as ○, and when the film thickness ratio before and after immersion is less than 95%, or N-methylpyrrolidone after immersion has some coloration, it is evaluated as Δ, when impregnated When a crack pattern or a pixel pattern peeled off from the substrate was observed, it was evaluated as ×.

Examples 2 to 12 and Comparative Examples 1 to 8

In the first embodiment, the radiation sensitive composition was prepared in the same manner as in Example 1 except that the type and content (parts by weight) of each component were replaced as shown in Table 3.

Then, various evaluations were carried out in the same manner as in Example 1 using the obtained radiation sensitive linear composition. The results are shown in Table 3.

In Table 3, each component is as follows.

C-1: 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one (trade name: IRGACURE 907, manufactured by Ciba Specialty Chemicals Co., Ltd.); C-2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)- 9.H.-carbazol-3-yl]-,1-(O-ethenylhydrazine) (trade name: IRGACURE OX02, manufactured by Ciba Specialty Chemicals Co., Ltd.); D-1: dipentaerythritol hexaacrylate (product) M-402, produced by East Asia Synthetic Co., Ltd.); D-2: a mixture of dipentaerythritol pentaacrylate and monoester of succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, Produced by East Asia Synthetic Co., Ltd.; D-3: pentaerythritol tetraacrylate (trade name M-450, manufactured by Toagosei Co., Ltd.); EEP: 3-ethoxypropionate ethyl ester; MBA: 3-methoxybutyl Acetate.

As is clear from Table 3, the radiation sensitive composition of the present invention containing the component (B) [polymer having an oxetane group and a polymerizable unsaturated bond] has sufficient development resistance even under low exposure. And the solvent resistance is also excellent. In contrast, a radiation-sensitive composition containing a copolymer having only one of an oxetane group and a polymerizable unsaturated bond, or a copolymer containing no oxetane group Radiation-linear composition, development resistance and solvent resistance are not good enough. Further, it is understood that the alkali-soluble resin is more preferably added, and the polymerizable unsaturated bond of the component (B) is more preferably a (meth) acrylonitrile group than the allyl group. Further, it is also known that the color filter formed using the radiation sensitive composition of the present invention has a high voltage holding ratio.

Claims (8)

A radiation sensitive composition for forming a coloring layer, characterized by comprising (A) a colorant, (B) a polymer having an oxetane group and a polymerizable unsaturated bond on a side chain, and (C) light Polymerization initiator. A sensitizing radioactive composition for coloring layer formation according to the first aspect of the invention, wherein (B) a polymer having an oxetane group and a polymerizable unsaturated bond on a side chain is an oxetane group And (meth)acrylonitrile-based polymers. The radiation-sensitive composition for forming a color layer according to claim 1 or 2, wherein (B) the polymer having an oxetane group and a polymerizable unsaturated bond on a side chain is selected from (B) -1) reacting a copolymer containing (b1) a polymerizable unsaturated compound having an oxetanyl group and (b2) a polymerizable unsaturated compound having a hydroxyl group with (b3) an unsaturated isocyanate compound The obtained polymer, (B-2), a copolymer comprising (b1) a polymerizable unsaturated compound having an oxetane group and a monomer composed of (b4) an unsaturated carboxylic acid, and (b5) having a ring a polymer obtained by reacting an oxyethylene group-containing polymerizable unsaturated compound, and (B-3) containing (b1) a polymerizable unsaturated compound having an oxetanyl group and (b5) having an oxirane group At least one of the group consisting of a copolymer of a monomer composed of a polymerizable unsaturated compound and a polymer obtained by reacting (b4) an unsaturated carboxylic acid. The sensitizing radioactive composition for forming a color layer according to claim 1 or 2, further comprising (D) a monomer having a polymerizable unsaturated bond. The sensitizing radioactive composition for forming a color layer according to claim 1 or 2, further comprising (E) an alkali-soluble resin (excluding the component (B) above). The sensitizing radioactive composition for forming a color layer according to claim 1 or 2, wherein the coloring agent (A) contains a group selected from the group consisting of CI Pigment Red 254, CI Pigment Green 58, and carbon black. At least one. A color filter comprising a coloring layer formed using the radiation sensitive composition for coloring layer formation according to any one of claims 1 to 6. A color liquid crystal display element comprising the color filter of item 7 of the patent application.