JP2010217872A - Colored radiation-sensitive composition, color filter, and color liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new colored radiation-sensitive composition capable of forming pixels that have a forward tapered shape and is superior in solvent resistance, even if it is low in light exposure. <P>SOLUTION: The colored radiation-sensitive composition contains (A) a coloring agent, (B) dispersant, (C) alkali-soluble polymer resin, (D) polyfunctional monomer, and (E) photoinitiator. At least either the (B) dispersant or the (D) polyfunctional monomer has a caprolactone structure, as well as, the (E) photoinitiator contains 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, There is known a method (see, for example, Patent Documents 1 and 2) of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape by radiation (hereinafter referred to as “exposure”) and developing.

  In the technical field of color filters in recent years, in addition to reducing the exposure amount and shortening the tact time, in order to meet the demand for high color purity for color liquid crystal display elements, The content ratio of the pigment in the radiation-sensitive composition tends to be higher. Under such circumstances, the cross-sectional shape of the pixel pattern is inversely tapered (overhang), and transparent electrodes such as ITO formed on the pixel pattern are disconnected, and the solvent resistance of the pixel is reduced. Has become apparent. However, an effective means for solving these problems has not yet been found.

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

  The present invention has been made on the basis of the circumstances as described above, and its problem is a novel coloring that can form a pixel having a forward tapered shape and excellent solvent resistance even at a low exposure amount. The object is to provide a radiation-sensitive composition.

  As a result of intensive studies, the present inventors have solved the above problem by incorporating a dispersant or polyfunctional monomer having a caprolactone structure in a colored radiation-sensitive composition and a specific photopolymerization initiator. The inventors have found that this can be solved, and have completed the present invention.

That is, the present invention is a colored radiation-sensitive composition containing (A) a colorant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photopolymerization initiator, (D) The polyfunctional monomer has a caprolactone structure, and (E) the photopolymerization initiator is 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholino The present invention provides a colored radiation-sensitive composition characterized by containing phenyl) butan-1-one.
The present invention also provides a colored radiation-sensitive material containing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photopolymerization initiator. It is a composition, (B) the dispersant has a caprolactone structure, and (E) the photopolymerization initiator is 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- The present invention provides a colored radiation-sensitive composition characterized by containing morpholinophenyl) butan-1-one.

The present invention also provides a color filter comprising a colored layer formed using the colored radiation-sensitive composition, and a color liquid crystal display device comprising the color filter.
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

By using the colored radiation-sensitive composition of the present invention, a pixel having a forward tapered shape and excellent solvent resistance can be formed even with a low exposure amount.
Therefore, the colored radiation-sensitive composition of the present invention is used in various applications including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for the production of color filters.

It is a schematic diagram which shows the cross-sectional shape of a pixel pattern.

Hereinafter, the present invention will be described in detail.
Colored radiation-sensitive composition Colored radiation-sensitive composition of the present invention (hereinafter, simply referred to as “radiation-sensitive composition”).
) Will be described.

-(A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment. Since the color filter is required to have heat resistance, the colorant in the present invention is preferably an organic pigment or an inorganic pigment.
Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (C.I. ) Names can be mentioned.

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

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

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

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

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

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

These colorants may be used by modifying the particle surface with a resin, if desired.
Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. For example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, etc. disclose the method of resin coating on the surface of carbon black.
The colorants can be used alone or in admixture of two or more.

When the radiation-sensitive composition of the present invention is used for the formation of a pixel, since the pixel is required to have a high-definition color, (A) the colorant is preferably a colorant with high color developability. Organic pigments are preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).

  The radiation-sensitive composition of the present invention has a forward tapered shape and solvent resistance even when the content of the colorant is 30% by weight or more in the total solid content of the radiation-sensitive composition. Excellent pixels can be formed. In the present invention, the upper limit of the content of the colorant is preferably 70% by weight or less, particularly preferably 60% by weight or less, in the total solid content of the radiation-sensitive composition, from the viewpoint of ensuring developability. . Here, solid content is components other than the solvent mentioned later.

-(B) Dispersant-
The radiation-sensitive composition of the present invention contains at least one of (B) a dispersant having a caprolactone structure and (D) a polyfunctional monomer having a caprolactone structure described later. Thereby, a forward tapered pixel can be formed even with a low exposure amount.
The dispersant having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, but is preferably a polymer dispersant having a polycaprolactone chain in the main chain or side chain. In this case, the molecular weight of the polycaprolactone chain is preferably 100 or more, more preferably 200 or more, and particularly preferably 200 to 5,000 from the viewpoint of enhancing a desired effect.

Examples of the polymer dispersant having a polycaprolactone chain include a graft polymer obtained by reacting poly (alkyleneimine) or poly (allylamine) with polyε-caprolactone, and a (meth) acrylic monomer having a polycaprolactone chain. Examples thereof include a polymer, a phosphate ester having a polycaprolactone chain, and a branched urethane resin having a polycaprolactone chain. More specifically, JP-A-61-174939, JP-A-9-169821, JP-A-2000-95827, JP-A-2000-95992, JP-A-2000-104005, JP-A-2007. -231106 gazette, Unexamined-Japanese-Patent No. 2007-269873 gazette etc. can be mentioned.
The polymer dispersant having a polycaprolactone chain can also be obtained commercially, and examples thereof include Addisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.).
In this invention, the dispersing agent which has a caprolactone structure can be used individually or in mixture of 2 or more types.

In the radiation-sensitive composition of the present invention, when a polyfunctional monomer (D) having a caprolactone structure is used and a dispersant having a caprolactone structure is not used, a cationic system, an anion having no caprolactone structure An appropriate dispersant such as a non-ionic, nonionic or amphoteric can be used. Examples of such a dispersant include a modified acrylic copolymer, an acrylic copolymer, polyurethane, and an alkylammonium salt or a phosphate ester salt of a polymer copolymer. In this invention, the dispersing agent which does not have a caprolactone structure can be used individually or in mixture of 2 or more types.
Of course, these dispersants having no caprolactone structure may be used in combination with the dispersant having a caprolactone structure.

In this invention, content of a dispersing agent is 0.5-100 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. is there. In this case, when there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.
In addition, when a dispersant having a caprolactone structure is used without using the (D) polyfunctional monomer having a caprolactone structure, the content is preferably in the total dispersant from the viewpoint of enhancing the desired effect. Is 25% by mass or more, more preferably 50% by mass or more.

  In the present invention, a dispersing aid can be used in combination with the dispersing agent. Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

-(C) Alkali-soluble resin-
The (C) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is not particularly limited as long as it is soluble in an alkali developer used in the development processing step when forming the colored layer. Although not intended, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among these, it is preferable to contain a polymer having a carboxyl group (sometimes referred to as a “carboxyl group-containing polymer”). As the polymer, for example, an ethylenically unsaturated group having one or more carboxyl groups. A monomer (hereinafter sometimes referred to as “unsaturated monomer (c1)”) and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (c2)”). And a copolymer thereof may be mentioned.

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate and the like. These unsaturated monomers (c1) can be used alone or in admixture of two or more.
In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) is preferably 5 to 50% by mass, more preferably 10 to 10% by mass. 40% by mass. By copolymerizing the unsaturated monomer (c1) within such a range, a radiation-sensitive composition having excellent alkali developability can be obtained.

Examples of the unsaturated monomer (c2) include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene and p-hydroxy-α-methylstyrene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl Ethylene oxide of (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, paracumylphenol Unsaturated carboxylic esters such as modified (meth) acrylates;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (c2) can be used alone or in admixture of two or more.

  Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, JP-A-7-140654, JP-A-10-31308, and JP-A-10-300922. And copolymers disclosed in JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-11-140144, JP-A-2008-181095, etc. As disclosed, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as the alkali-soluble resin.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 100,000, preferably. Is 3,000 to 50,000. In this case, if the Mw is too small, the remaining film rate of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and the electrical characteristics may be deteriorated. There is a risk that the pattern may be lowered, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.
In addition, the ratio (Mw / Mn) of Mw of the alkali-soluble resin in the present invention to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is , Preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  The alkali-soluble resin in the present invention can be produced by a known method. For example, it is disclosed in JP 2003-222717 A, JP 2006-259680 A, WO 07/029871 pamphlet, and the like. The structure, Mw, and Mw / Mn can also be controlled by the existing method.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
In this invention, content of alkali-soluble resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. In this case, if the content of the alkali-soluble resin is too small, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed portion of the substrate or on the light shielding layer. However, since the pigment concentration is relatively lowered, it may be difficult to achieve a target color concentration as a thin film.

-(D) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds. The radiation-sensitive composition of the present invention contains at least one of a dispersant having a caprolactone structure and a polyfunctional monomer having a caprolactone structure, but contains a polyfunctional monomer having a caprolactone structure. More preferably.

  The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying (meth) acrylic acid and ε-caprolactone with polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, etc. Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

In the radiation-sensitive composition of the present invention, when a dispersant having a caprolactone structure is used and a polyfunctional monomer having a caprolactone structure is not used, an appropriate polyfunctional monomer having no caprolactone structure is used. Can be used. In addition, it is preferable to use a polyfunctional monomer having no caprolactone structure together with a polyfunctional monomer having a caprolactone structure from the viewpoint of increasing the remaining film ratio. As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene;
Tris [2- (meth) acryloyloxyethyl] phosphate,
Isocyanuric acid ethylene oxide modified triacrylate;
Examples thereof include poly (meth) acrylate having a urethane structure.

Among these polyfunctional monomers not having a caprolactone structure, poly (meth) acrylates of polyhydric alcohols having 3 or more valences, dicarboxylic acid modified products thereof, and poly (meth) acrylates having a urethane structure are included. preferable. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Monoesterified products of acrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified product of hexaacrylate, pentaerythritol triacrylate and succinic acid, monoesterified product of dipentaerythritol pentaacrylate and succinic acid has high strength of the colored layer, excellent surface smoothness of the colored layer, and unexposed This is preferable in that ground stains, film residue, and the like hardly occur on the substrate and the light shielding layer.
In this invention, the polyfunctional monomer which does not have a caprolactone structure can be used individually or in mixture of 2 or more types.

Content of the polyfunctional monomer in this invention is 20-400 mass parts normally with respect to 100 mass parts of (B) alkali-soluble resin, Preferably it is 50-300 mass parts. By setting the content of the polyfunctional monomer in such a range, a colored layer excellent in strength, surface smoothness and solvent resistance can be formed, and radiation sensitivity excellent in alkali developability can also be formed. Sex composition can be obtained.
Moreover, when using the polyfunctional monomer which has a caprolactone structure without using the dispersing agent which has a caprolactone structure, the content rate is 10 in all the polyfunctional monomers from the point which raises a desired effect. It is preferable that it is mass% or more.

-(E) Photopolymerization initiator-
The photopolymerization initiator in the present invention generates an active species capable of initiating polymerization of the (D) polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.
In the present invention, the photopolymerization initiator contains 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one. By forming the photopolymerization initiator in combination with the dispersant having the caprolactone structure and / or the polyfunctional weight having the caprolactone structure, a pixel having a forward tapered shape and excellent solvent resistance is formed. Is possible. The content ratio is preferably 25% by mass or more in the total photopolymerization initiator from the viewpoint of improving the solvent resistance of the colored layer.

  In the present invention, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and a group consisting of a thioxanthone compound and an O-acyloxime compound Surprisingly, the desired effect can be further enhanced by using at least one selected from the above. As a thioxanthone type compound, the compound represented by following formula (4) can be mentioned, for example.

(Wherein, R ² to R ⁵ are mutually independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms.)

In the above formula (4), R ² and R ⁴ are preferably a hydrogen atom, and R ³ and R ⁵ are preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms. Furthermore, as R < ³ > and R < ⁵ >, it is preferable that both are C1-C6 alkyl groups.
Specific examples of the thioxanthone compound represented by the above formula (4) include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc. can be mentioned.
Of these thioxanthone compounds, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone are preferable, and 2,4-diethylthioxanthone is particularly preferable.

In the present invention, the thioxanthone compounds can be used alone or in admixture of two or more.
From the standpoint of enhancing the desired effect, the blending mass ratio of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the thioxanthone compound is The ratio is preferably 1: 1 to 20: 1, more preferably 2: 1 to 15: 1.

The O-acyloxime compound is not particularly limited as long as it is a photopolymerization initiator having an acyloxime structure (> C═N—O—CO—). For example, International Publication No. WO2002 / 100903 No. pamphlet, International Publication No. 2006/018933 pamphlet, International Publication No. 2008/078678 pamphlet and the like. Preferable specific examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
In the present invention, the O-acyloxime compounds can be used alone or in admixture of two or more.
From the standpoint of further enhancing the desired effect, the blending mass of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and an O-acyloxime compound The ratio is preferably 1: 1 to 20: 1, more preferably 1: 1 to 10: 1.

In the present invention,
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, etc. Acetophenone compounds other than 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one;
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole;

2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (can also be used trichloromethyl) known photopolymerization initiator of triazine compounds such as -s-triazine.

  4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylamino A known sensitizer such as 2-ethylhexyl benzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone is used in combination. You can also.

  In this invention, content of a photoinitiator is 0.01-120 mass parts normally with respect to 100 mass parts of (D) polyfunctional monomers, Preferably it is 1-100 mass parts, More preferably 1 to 70 parts by mass. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for a colored layer to fall off from a board | substrate at the time of image development.

-Additives-
Although the radiation sensitive composition of this invention contains the said (A)-(E) component, it can further contain another additive as needed.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anti-aggregation agents such as sodium acrylate; Residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (me A) Development improver such as acrylate.

-Solvent-
The radiation-sensitive composition of the present invention contains the components (A) to (E) as essential components, and optionally contains the additive component, but is usually prepared as a liquid composition by blending a solvent. The
As the solvent, as long as the components (A) to (E) and the additive component constituting the radiation-sensitive composition are dispersed or dissolved and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

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

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

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 -Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate, 1,3-butylene glycol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate Formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

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

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is 5 from the viewpoint of the coating property and storage stability of the resulting radiation-sensitive composition. An amount of ˜50 mass% is preferred, and an amount of 10˜40 mass% is particularly preferred.

Method of forming a color filter Then, using a radiation-sensitive composition of the present invention, a method for forming a color filter of the present invention.
The method for forming a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) A step of post-baking the developed coating film.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light shielding layer (black matrix) is formed so as to partition a portion for forming a pixel, and, for example, a red (A) colorant is contained on the substrate. The radiation-sensitive composition of the present invention is usually applied as a liquid composition, and then pre-baked to remove the solvent by evaporation to form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition to the substrate, an appropriate coating method such as a spin coating method, a casting coating method, a roll coating method, or a coating method using a slit die coater can be employed. A coating method using a slit die coater is preferred.
Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70 degreeC to 110 degreeC normally for about 1 to 10 minutes.
The coating thickness is usually 1.0 to 10 μm, preferably 1.0 to 8.0 μm, particularly preferably 1.0 to 6.0 μm as the film thickness after pre-baking.

-(2) Process-
Thereafter, at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern.
Examples of radiation light sources used for exposure include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and other lamp light sources, argon ion lasers, YAG lasers, Examples thereof include a laser light source such as a XeCl excimer laser and a nitrogen laser, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is usually 10~10,000J / m ^2. According to the radiation-sensitive composition of the present invention, a pixel having a forward taper shape and excellent solvent resistance can be formed even with an exposure amount of 800 J / m ² or less, and even with an exposure amount of 600 J / m ² or less. it can. The lower limit of the exposure amount is preferably 100 J / m ² or more from the viewpoint of controllability when a light source with high illuminance is used.

-(3) Process-
Then, it develops using a developing solution, Preferably an alkaline developing solution, The unexposed part of a coating film is dissolved and removed.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 10 to 300 seconds at room temperature.

-(4) Process-
Thereafter, a post-baked coating film after development can provide a substrate on which red pixel patterns made of a cured product of the radiation-sensitive composition are arranged in a predetermined arrangement.
The post-baking conditions are preferably 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Furthermore, by repeating the steps (1) to (4) using a green radiation-sensitive composition containing a green (A) colorant, a green pixel pattern is formed on the same substrate, and further blue (A) Using the blue radiation-sensitive composition containing the colorant, the steps (1) to (4) are repeated to form a blue pixel pattern on the same substrate, whereby red, green A pixel array in which pixel patterns of three primary colors of blue and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.
A black matrix can be formed by performing the said (1)-(4) process using the black radiation sensitive composition containing a black (A) coloring agent.

Color Filter The color filter of the present invention has pixels and / or a black matrix formed as described above from the radiation-sensitive composition of the present invention.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
On the color filter formed as described above, after forming a protective film as necessary, a transparent conductive film is formed by sputtering. Examples of the transparent conductive film include an ITO film made of indium oxide-tin oxide, an IZO film made of indium oxide-zinc oxide, and the like. Since the cross-sectional shape of the pixel pattern formed using the radiation-sensitive composition of the present invention is a forward taper, the transparent electrode does not break. Therefore, a high-quality color liquid crystal display element having excellent electrical characteristics can be produced.
Further, as one form of the color liquid crystal display element of the present invention, the colored radiation-sensitive composition of the present invention is used to form pixels and / or a black matrix as described above on a thin film transistor substrate array. A color liquid crystal display element having particularly excellent characteristics can be produced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Synthesis of dispersant having caprolactone structure Synthesis Example 1
In a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet and a reflux tube, 10.0 parts by mass of 12-hydroxystearic acid (manufactured by Junsei Chemical) and 190 parts by mass of ε-caprolactone (manufactured by Junsei Chemical) are charged. The temperature was raised to 160 ° C. over 4 hours under a nitrogen stream, heated at 160 ° C. for 2 hours, and then heated until the remaining amount of ε-caprolactone was 1% or less. Then it was cooled to room temperature. The polyester contained in this reaction solution had a number average molecular weight of 2580 and an acid value of 21.0 mg KOH / g.
Next, a mixture of 114.6 parts by mass of xylene and 70 parts by mass of poly (allylamine) 10% aqueous solution (“PAA-1LV” manufactured by Nitto Boseki Co., Ltd., number average molecular weight of about 3000) was stirred at 160 ° C. in the reaction flask. Then, water was distilled off using a separator, and xylene was returned to the reaction solution (confirmed that 50% by weight of water had been distilled off), and the reaction solution 69. 59 parts by mass of the mixture heated up to 160 ° C. was added and reacted at 160 ° C. for 2 hours. Thus, a solution (solid content concentration = 40.1%) containing a poly (allylamine) dispersant having a polycaprolactone chain in the side chain was obtained. This dispersant is referred to as “dispersant (B-1)”. Dispersant (B-1) had an amine value of 10.5 mg KOH / g and an acid value of 19.8 mg KOH / g.

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Red 254 (trade name BK-CF, manufactured by Ciba Specialty Chemicals) /C.I. I. Pigment Red 177 (manufactured by Ciba Specialty Chemicals, trade name A3B) /C.I. I. Pigment Yellow 150 = 40/40/20 (weight ratio) 20 parts by mass of the mixture, 5 parts by mass of the dispersant (B-1) as the dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate as the solvent having a solid content concentration A pigment dispersion (R1) was prepared by treating with a bead mill using 25%.

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 50/50 (weight ratio) 20 parts by mass of the mixture, 5 parts by mass of the dispersant (B-1) as the dispersant (in terms of solid content), and 25% of the solid content concentration of propylene glycol monomethyl ether acetate as the solvent And a pigment dispersion (G1) was prepared by processing with a bead mill.

Preparation Example 3
A pigment dispersion (R2) was prepared in the same manner as in Preparation Example 1 except that Disperbyk-2000 (manufactured by BYK Corporation), which is a modified acrylic copolymer having no polycaprolactone chain, was used as the dispersant. Prepared.

Preparation Example 4
The same procedure as in Preparation Example 2, except that a urethane resin having an amine value of 14 mg KOH / g and a weight average molecular weight of 24,000 containing 53% by mass of a copolymer unit derived from ethylene oxide and propylene oxide was used as the dispersant. Thus, a pigment dispersion (G2) was prepared.

Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid, 35 parts by mass of benzyl methacrylate, and acenaphthylene. 30 parts by mass, 10 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of ω-carboxypolycaprolactone monoacrylate, and 5 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (chain transfer agent) were prepared. Replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization to obtain a copolymer solution. The obtained resin had Mw = 11,000, Mn = 5,000, and solid content concentration = 31.0%. This copolymer is referred to as “alkali-soluble resin (C-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 800 parts by mass of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the flask, and at the same temperature, 60 parts by mass of styrene, 60 parts by mass of methacrylic acid, and methyl methacrylate. A mixture of 65 parts by mass, 65 parts by mass of butyl methacrylate, and 10 parts by mass of azobisisobutyronitrile was added dropwise over 1 hour, and further reacted at 100 ° C. for 3 hours, and then 2 parts by mass of azobisisobutyronitrile. A solution in which 50 parts by mass of cyclohexanone was dissolved was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a copolymer solution. After cooling to room temperature, about 2 g of the copolymer solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was adjusted so that the nonvolatile content of the previously synthesized copolymer solution was 20%. Was added to prepare a copolymer solution. The obtained resin had Mw = 40,000 and Mn = 15,000. This copolymer is referred to as “alkali-soluble resin (C-2)”.

Example 1
100 parts by mass of pigment dispersion (R1), (C) 10 parts by mass (as solid content) of alkali-soluble resin (C-1) as alkali-soluble resin, and (D) dipentaerythritol hexaacrylate 15 as polyfunctional monomer Parts by mass, (E) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator , Trade name Irgacure 379) and 5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed so that the solid concentration was 25% by weight to prepare a liquid composition (S-1).

  The liquid composition (S-1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

Evaluation of the cross-sectional shape After applying the liquid composition (S-1) on the surface of the glass substrate using a spin coater, pre-baking was performed for 4 minutes on a 90 ° C. hot plate to apply a coating having a thickness of 2.0 μm. A film was formed. Subsequently, after cooling this board | substrate to room temperature, the coating film on a board | substrate was exposed by the exposure amount of 400 J / m < ² > through the photomask using the high pressure mercury lamp. Thereafter, shower development was performed by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds. Next, post-baking was performed at 220 ° C. for 30 minutes to form a 90 μm stripe pixel pattern on the substrate.
Next, the cross-sectional shape of the obtained pixel pattern was observed with a scanning electron microscope, and the taper angle shown in FIG. 1 was measured. If the taper angle is 80 degrees or more, the transparent electrode film may be disconnected. The ideal taper angle is 30 to 70 degrees.

Evaluation of solvent resistance The liquid composition (S-1) was applied on the surface of a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2.0 μm. A coating film was formed. Subsequently, after cooling this board | substrate to room temperature, the coating film on a board | substrate was exposed by the exposure amount of 400 J / m < ² > through the photomask using the high pressure mercury lamp. Thereafter, shower development was performed by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds. Next, post-baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.
Next, the obtained substrate was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, the case where the dot pattern was retained after the immersion and the N-methylpyrrolidone after the immersion was not colored at all, the dot pattern was retained after the immersion, but the N-methylpyrrolidone after the immersion was slightly colored The dot pattern peeled off from the substrate after immersion was observed and the case where N-methylpyrrolidone after immersion was colored was evaluated as x.

Evaluation of Remaining Film Ratio The liquid composition (S-1) was applied on the surface of the glass substrate using a spin coater, and then pre-baked on a 90 ° C. hot plate for 4 minutes to obtain a film thickness of 1.3 μm. A coating film was formed. Subsequently, after cooling this board | substrate to room temperature, the coating film on a board | substrate was exposed by the exposure amount of 400 J / m < ² > through the photomask using the high pressure mercury lamp. Then, after performing shower development by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds, Post-baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern.
Next, the residual film ratio (film thickness after post-baking × 100 / 1.3) was calculated by observing the dot pattern on the obtained substrate with a scanning electron microscope and measuring the film thickness. It can be said that the higher the remaining film ratio, the better the sensitivity.

Examples 2 to 15 and Comparative Examples 1 to 7
Liquid compositions (S-2) to (S-22) were prepared in the same manner as in Example 1 except that the types and amounts of the components of the liquid composition were as shown in Table 1.
Subsequently, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-22) were used instead of the liquid composition (S-1). The results are shown in Table 2.

In Table 1, each component is as follows.
D-1: Dipentaerythritol hexaacrylate D-2: In the above formulas (1) to (3), m = 1, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms (Brand name KAYARAD DPCA-60, Nippon Kayaku Co., Ltd.)
D-3: a compound in which m = 2 in the above formulas (1) to (3), the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms (trade name KAYARAD DPCA-120, Japan (Made by Kayaku)
E-1: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (product name, Irgacure 379, manufactured by Ciba Specialty Chemicals)
E-2: 2,4-diethylthioxanthone E-3: 4,4′-bis (diethylamino) benzophenone E-4: 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butane 1-on (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
E-5: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
E-6: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name Irgacure OXE02, Ciba Specialty・ Made by Chemicals
E-7: 1,2-octadione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) (trade name Irgacure OXE01, manufactured by Ciba Specialty Chemicals)

As is apparent from Table 2, at least one of (B) the dispersant and (D) the polyfunctional monomer is a component having a caprolactone structure (the pigment dispersion is R1 or G1, and the component (D) is D- 2 or D-3), and the photopolymerization initiator includes 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (E-1) In the colored radiation-sensitive composition of the present invention, the formed pixel pattern had a forward taper shape, excellent solvent resistance, a high residual film ratio, and good sensitivity.
On the other hand, when neither (B) the dispersant nor (D) the polyfunctional monomer contains a component having a caprolactone structure, or when the photopolymerization initiator does not contain (E-1), The obtained pixels were inversely tapered or the solvent resistance was poor.

Claims (7)

  A colored radiation-sensitive composition comprising (A) a colorant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photopolymerization initiator, wherein (D) a polyfunctionality The monomer has a caprolactone structure, and (E) the photopolymerization initiator is 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1- A colored radiation-sensitive composition characterized by containing ON. A colored radiation-sensitive composition containing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photopolymerization initiator, (B) The dispersant has a caprolactone structure, and (E) the photopolymerization initiator is 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane- A colored radiation-sensitive composition comprising 1-one.   The colored radiation-sensitive composition according to claim 1 or 2, wherein (E) the photopolymerization initiator further contains at least one selected from the group consisting of a thioxanthone compound and an O-acyloxime compound.   The colored radiation-sensitive composition according to claim 3, wherein the thioxanthone compound is 2,4-diethylthioxanthone.   The color filter provided with the colored layer formed using the colored radiation-sensitive composition in any one of Claims 1-4.   A color liquid crystal display device comprising the color filter according to claim 5. The manufacturing method of a color filter including the process of forming a colored layer with the exposure amount of 800 J / m < ² > or less using the colored radiation-sensitive composition in any one of Claims 1-4.

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